SA97180735B1 - cycloentadienyl 3-heteroatom ubsttutedcontaining metal complexes and olefin polymerization - Google Patents

Abstract

Abstract: This invention relates to heteroatom-substituted ligands containing cyclopentadienyl, metal complexes containing these ligands and catalyst systems prepared from catalyst components incorporating these metal complexes. Metal complexes contain either a Cp-heteroatom bond or a Cp-heterocyclic bond at position 3 of the Cp. In preferred metal complexes, the ligand represents an indenyl group with a 3-atom other than a homogeneous substituted 3-heteroatom. Catalytic systems can be used for olefin polymerization at high temperatures that are highly active and produce a polymer with a high molecular weight.

Description

3-HETEROATOM SUBSTTUTED CYCLOPENTADIENYL Contains metal complexes and olefin polymerization Full description Background of the invention This invention relates to a type of metal complexes; As well as the ligands used to prepare those complex metal compounds, indenyl, and the catalysts for the polymerization of olefin polymerization catalysts derived from them, which are particularly suitable 0 for use in a polymerization process to prepare polymers by polymerizing x - olefins olefins and mixtures of alpha-olefins .colefins Metal complexes of restricted geometry and methods for their preparation are described in US Patent Application Serial No. 407; 046; deposited on ¥ July; 0l (Patent Euro-A-815; £37)(" USPatent Application Serial No. 7178; 0 047; Filed ¥ Jul + 19900 (Patent Euro-A-651 468); the USPAT application which Has serial £V0; 707 ; filed May 01 + 1991 (EP = H 878 016); US patent application having serial number AVL ¢ TIA filed May 1 11497 .(European Patent A-777; + (OF) and US Patent Application Serial No. 807 Filed in 1947 Reyani 71 (Pat. 4 17/191); plus 0 also US Patent Applications with Numbers 118 0 + ¢ 0 (fly to 0) AY write in Kadif (TE © 2/77/7850; and international patent 198/0 OY f. The contents of all such prior patents or corresponding US patent applications are listed here at US Patent Nos. 5/75/8197 and 4/114 5/70 describe zirconium-complexes having cross-linked metallocene ligands where two indenyl groups are covalently linked together by A bridge bond containing carbon or silicon that is useful for the polymerization of propylene v is unsymmetrical containing CP and shows the European patent A- 077/5781 metalloacetate from bis with substituents of different atoms. fluorene On Ligand and Fluorine

E.Barsties, 5. Schaible, M.- H.Prosenc, U.Rief, W.Roll 0. Weyland, 3. 1 and Pine H. Plenio, Wii Dorerer, H-H. Brintzinger J. Ogranometallic Chem. 1996 520, 63-68 Brith J. Ogranometallic Chem. 1996, 519, 269-272 © 0. Systems in which the cyclopentadienyl ring of indenyl is substituted by a dimethylamino sid group in an unconjugated indenyl repeat, which is bridged via Si. (Silicon) Useful for the formation of polypropylene and polyethylene It is isomorphic (substituted on one side). R. Leino, H. J. K. Luttikhedde, P. Lehmus, C.- E. Weilen, R. Sjoholm, A. Weiben 1

Lehtonen, J. Seppala, 111. Nasman Macromolecules, 1997, 30, 3477/3488 oxygen with C2 oxygen bridged by indenyl metallosunate from bis-indinella

I.M.Lee, W.J. Gauthier, J. 14. ¢ indenyl from group 1 indenyl shows in situ metallocenes Ball 3. leynger, S. Collins Organometallics, 1992, 11, 3225-2122 10 bis-indenyl bound metallocenes Arrayed by C2 with oxygen 0 in positions A “©; of the lain ¢ indenyl complex, N. Pioccolravazzi, P. Pino, ©. Consiglio, A, Sironi, M. Moret Oranomenetallics 1990, 9, 3098-3105 metallocenes from a non-bent indenyl bis with oxygen in both positions; WA from the indelyl group. carbon He believed that replacing an atom is a violation; In contrast to the carbon substitution, Y. metallocene at any position of the indelinyl group of the meptalocene compound, “HJ” makes the complex olefin polymerization; When used in a catalyst for olefin polymerization the catalyst is less effective i.e.; There will be a lower yield for polymerization by olefins; The resulting polymer has a lower molecular weight than the Yo-x polymerization packing (the stereochemical arrangement of the main chain units in the polymer is less. It has been suggested that the low reactivity of this type of broad

¢ Catalysts refer to the special interaction between the lone pair electrons of the offending atom with a polymerization activator from a catalyst or conjugate in the form of a Lewis acid; Which leads to a Cp ring whose electron reactivity is more Jad and which Lad has more stereoisomer obstruction. See P.

Foster M.

D.

Rausch, J.

C.

W.n-BuLi Chein.

J.

Ogranometallic Chem. 1996, 519, 0 269-272.

The detection of random atom substitution was found in violation in monomeric metallocenes Cp 0601106605 in EP-A-4116/8106; International Patent ©0177 – International Patent 178749/96 and US Patent Nos. JAY 87+[

/1711 AY 40 0 and related cases.

01 So far it has been believed that substitution by the offending atom in the complex metallocene compounds used as polymerization catalysts has disadvantages due to undesirable interactions led and pair electrons of the offending atom either with the transitional atom of the same metallocene molecule or to a different metallocene molecule ¢ or with other components of the catalyst system.

Vo and many modifications have been made in the various complex metallocene compounds used as catalysts for olefin polymerization. any way ; There are problems still exist with regard to the efficiency of warming or inactivation of the catalyst under conditions of polymerization at a high temperature. It is preferable to be able to produce olefins with high molecular weights. It is also desirable that other physical properties can be improved

0 - for polymers produced by a change of substitution around the cyclopentadienyl group

metallocene complexes for cyclopentadienyl -olefin polymerization used as catalyst systems in olefin polymerization General description of the invention: According to the formula metal complexe according to this invention; Complex metallic compounds are supplied

° —)® Hala RP p

where

4 is a metal from groups 9 through VY of the periodic table of elements; the lanthanides;

4+ which is in the original oxidation state + 7 + or actinides or actinides lanthanides cyclic Juda with penta group (Ti) and is linked by pi electrons ©

JI (Cp) cyclopentadienyl is a cyclic ligand group; Fazal

Its centralization is linked by its Ti electrons © substituents: RA ; J Cus (RB) JT is a

ia ¢ 1, 7; 102; 280 and 2; where e; 108; 26 and eile Rp 7 sets;

Whereas -7 is an offending atom that is covalently bonded to the Cp ring ; and b RB where J 0 is 1 ohm; and when [ equals zero lic 7 it is 17 01 ; 3:8; or 1

; and when [ - 01, 1 is © or 5; Or JIN 7 and 88 have a bond

double linked by 7; and when [- of , 7 is 17 or © ; and where

SRP - separately when each occurrence is hydrogen; or phrase

A group with from 1 to 860 nonhydrogen atoms that is 00 is hydrocarbyl or hydrocarbylsilyl or hydrocarbic

Hydrocarbyl replaced with a halogen or hydrocarbyl with hydrocarbylox

hydrocarbyloxy or hydrocarbyl replaced by hydrocarbyl amino

hydrocarbylsilyl hydrocarbyl silyl or hydrocarbylamino

or a hydrocarbylamino or di (hydrocarbyl amino) 0 “hydrocarbyloxy; each RB is substituted

Optionally, with one or more groups that are at each occurrence of a hurricane

hydrocarbyloxy or hydrocarbylsiloxy or

hydrocarbylsilylamino sis; Di(hydrocarbylsilyl)amino

di(hydrocarbylsilyl)amino or hydrocarbyl amino or

di (hydrocarbylsilyl amino sud; or di(hydrocarbyl)phospheno

di(hydrocarbyl)phosphino or hydrocarbylsulfido + or hydrocarbylsulfido

hydrocarbyl or hydrocarbyl substituted with a halogen or hydrocarbyl

hydrocarbyl or hydrocarbyloxy substituted with hydrocarbyl 0

inferred by hydrocarbylamino or hydrocarbyl Ju Ss” or

hydrocarbylsilyl hydrocarbyl hydrocarbyl has a 1 to Y atom

nonhydrogen; a ; A non-overlapping group of 1 to 10 non-atoms

hydrogen And each of the RA; RC; RD is hydrogen; or a group of them

0. From 1 to 80 non-hydrogen atoms that are either a halo-substituted hydrocarbyl or

A hydrocarbyl substituted with a hydrocarpyloxi or a hydrocarbyl substituted with a hydrocarbyl amino or

hydrocarbyl silyl or hydrocarbyl silyl hydrocarbyl; and each RA; RC; Ali we RD

Optionally join one or more groups that are separate at each occurrence of

hydrocarbilox, hydrocarbylsiloxy, or hydrocarbylsilylaminos; II (hydrocarbyl

(Jd ve amino or hydrocarbyl gud or di(amito hydrocarbyl); or di(hydrocarbyl)

Phosphino or hydrocarbyl sulfidohydrocarbyl or hydrocarbyl substituted for halo or hydrocarbyl

Substituted with a hydrocarbyloxy or a hydrocarbyl substituted with a hydrocarbyl amino or hydrocarbyl

silyl or hydrocarbyl silyl hydrocarbyl with 1 to 10 non-hydrogen atoms; or

a non-overlapping group with 1 to 10 non-hydrogen atoms ; or optionally both

RD (RC RB) groups are covalently bonded to each other to form one or more rings

Compact or cyclic systems have from 1 to 8 non-hydrogen atoms per R group and are

One or more embedded rings or ring systems are not replaced or replaced by one or more

More than one of the groups that, at each occurrence of it alone, are hydrocarpyloxes or

hydrocarbylsiloxy or hydrocarbylsilylamino; Di(Hydrocarbylsilyl)amino O

ve hydrocarbyl amino or di(hydrocarbyl amino); or di(hydrocarbyl)phospheno or

hydrocarbylsulfido hydrocarbylsulfido or hydrocarbyl substituted with halo or

A hydrocarbyl substituted with a hydrocarpyloxi or a hydrocarbyl substituted with a hydrocarbyl amino or F

hydrocarbyl silyl or hydrocarbyl silyl hydrocarbyl having 1 to 10 non-hydrogen atoms ; or a non-overlapping group containing from 1 to 10 atoms other than hydrogen ; Z is a bivalent moiety bound to both Cp and 14 by β- bonds; where Z includes boron ; or a member of the VE group of the periodic table of the elements »0, which also includes nitrogen ¢ phosphorus ; Sulfur or oxygen .oxygen X is a dianionic ligand or anionic ligand group with up to 0 atoms except for the type of ligands which are cyclic ligand groups linked with 11 electrons non-centred; 1 to not be separately at each occurrence of it is a compound of a neutral Lewis base with a number of up to 01 atoms; © is zero; 1a or 7 and is 1 less than in the al a oxidation state (M) and when x is an anionic ligand sled; and when x is a dianionic ligand group » 1 = P ; f: q Vo is zero; 1 or LY and the foregoing complexes may exist as optionally separated catalysts in the form or as mixtures with other complexes + in the form of any dissolved additive; optionally in a solvent; in particular an organic liquid; In addition, in the form of a dimer (a dimer) or a chelated derivative -;- (forming an ils complex that combines two compounds to a central YX ion); from him ; where the chelation binding agent is an organic substance »; The Lewis rule is neutral; Ad ayy especially trihydrocarbylamine ¢ trihydrocarbylphosphine; or a halogenated derivative thereof. Yes

A

also; According to this invention ¢ A catalyst system is prepared for the polymerization of the two millennium prepared from: Components of a catalyst system or including a complex metal compound of one of the aforementioned complex compounds catalyst (a) a catalyst component mentioned; and co-catalyst including co-activation catalyst where the molecular ratio ranges from: 001 (b) © component or activation (a) by using the 001:1 technique to 1:00.001 gram (a) to (b) of olefin polymerization Another embodiment of this invention is a system for the polymerization of olefins: prepared from the components of a catalyst system comprising (a) a catalyst component comprising a complex metal complex of one of the aforementioned complex 0 metal compounds; and metal complexes (b) a co-catalytic component that includes an activation catalyst with a molecular ratio of 1:001 to 1:00,000 gram (0) to (b) of the base. cation in the form of a cation metal complexe where the complex metal compound is olefins polymerization and also according to this invention a process is prepared for the polymerization of olefins Vo and under acolefins conditions comprising one contact a; more than one alpha - olefins polymerization by one of the catalyst systems aforementioned, and there is a preferred process for this invention, which is a process of polymerization in solution of a degree that includes contact with one or more alpha-olefins at high temperature to polymerize the olefins “clinking” and under conditions of polymerization by one or more of the previous catalyst systems 0 m to about 790 m. 001 mentioned it at a temperature ranging from about

Within the scope of this invention are polyolefin products which are produced by means of the aforementioned processes and the preferred products are those having a long chain displacement and a reverse engineered shape of the molecules. This invention prepares a ligand containing cyclopentadienyl© from the aforementioned complex metal compounds, where the ligand is in the form of: a) a free base with ¥ of protons from which the deprotons can be deprotonated; b) dilithium salt; c) magnesium salt; or 2) a binary anion treated with a single Sb «i silyl -mono or disilylated dianion ye. Within the scope of this aspect of the invention is the use of one of these ligands to prepare for the purpose of producing a metal complex belonging to this The invention “or for the preparation of © for the purpose of producing a complex metal compound that includes a metal from one of the groups “to 1” of the periodic table of the elements “lanthanides” or “actinides” and from “1 to” of the ligands These catalysts and processes result in highly effective production of high molecular weight olefin polymers under a wide range of polymerization conditions ¢ and particularly at elevated temperatures. They are particularly useful for in-solution polymerization or BSH softening polymerization propylene (slug yllfethylene (polymers) LESH polymerization of ethylene 1©06 lene: “EP pol for ethylene octene (5S s¥l/ethylene) (Eo polymers) polymers » ethylene styrene 0 (polymers “(ES polymers) propylene and ethylene 60:71606© / propylene / diene (EPDM polymers in which diene is 1 ethylidenenorbornene £—1,4-hexadiene or a similar unconjugated diene. The use of higher temperatures results in a sudden increase in the yields of these processes due to the fact that the increased solubility of the polymer from higher temperatures

1 allows the use of increased transformations (concentrating on the resulting polymer) without increasing the solution limits in polymerization equipment as well as lower energy costs for the automation of the volatility of the reaction product. The catalysts of the present invention may also be supported on a support material. In the moron or in phase olefin polymerization and used in olefin polymerization processes © We may pre-polymerize the catalyst with one or more monomers of 0 5 phase gaseous polymerization or in a separate process with Jolin 1650 H in place in olefin monomers. In advance, before the basic polymerization process, prepolymerized intermediate extraction of the polymerized catalyst, and so far it is believed that the replacement with the offending atom is direct on a group that is a cycloligand group »linked by (Cp) cycloptadaniyl 0 no metallocene complexes The delocalized electrons of the metallocene complex have a beneficial effect on the utilization of the believed compound in the olefin polymerization catalytic system. However; It was found that complex metallocene compounds. Olefin polymerization, the subject of this invention, which has a direct opposite atom substitution on one metallocene complexes linked by # electrons has extraordinary properties as Cp group Vo molecular weight Alle; Olefin catalysts allow the production of olefin catalys polymers at higher catalyst efficiencies. Led complex metallocene compounds with desirable properties are highly preferred. In the diagrams, dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1- shows the crystal structure -1 Fig. 7 ((1,2,3,3a,7a-1)-3- (1-piperidinyl)-1H-inene-1-yl)silanaminato-(2)-N-)-titanium. dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1- form ¥— showing the crystal structure ((1,2,3,3a,7a-1)-3-methoxy-1H-inene -1-yl)silanaminato-(2)-N-)-titanium.

AR

[N-(1,1-dimethylethyl)-1,1-dimethyl-1- Figure *- shows the crystal structure of ((1,2,3,3a,7a-7)-3-(1-piperidinyl) -1H-inene-1-yl)silanaminato-(2)1-)-N-(2,3,4,5-1)- 2,4-hexadiene)-titanium. : Detailed description ° All references to the periodic table of the elements here will refer to the periodic table of the elements; Published by and copyright 1989 CRC Press, Inc. Also; Any reference to a group or groups will be to the group or groups as reflected in this periodic table of the elements using the TUPAC group numbering system. aliphatic as used herein are olefins and olefins form Ve; In addition to vinylic compounds containing unsaturating vinyl aromatic or aromatic Cro Norbornene «cyclopentene; cyclobutene cyclobutene Jia cyclic N40 substituent in both positions norbomene; Containing norbornene Contains mixtures of these Lady. What is hydrocarbyl with hydrocarbyl groups and includes 0 Caso olefins in addition to your mixtures of those olefins with olefinic compounds 1 —£ ¢ \ « ethylene norbornene Examples of the latter compounds include torbornene ethene and the like; The 1,4-hexadiene catalysts and the processes herein are particularly suitable for use in the preparation of blended polymers of ethylene, 1-hexene/ethylene, or ethylene-1-butene. Butene -1 [ethylene or ethylene propylene / ethylene or ethylene styrene styrene [ ethylene 0 pentene -1- 4-methyl methyl —£ / ethylene or ethylene 1- pentene-1-pentene / ethylene plus 1-octene polypolymers | ethylene and ethylene 1-pentene propylene propylene ethylene terpolymers Unconjugated copolymers terpolymers; eg eg diene and diene . EPDM Ye va.

VY

Phosphines “carbon monoxide and the preferred group 72 we find carbon monoxide and trimethylphosphine, especially trimethylphosphine” dimethyl phosphines (0 = Y) and bis-triphenylphosphine or triethylphosphine is R' where » P(OR"); bis(1,2-dimethylphosphino)ethane and in particular ethers or a combination of them; silyl ethers or silyl hydrocarbyl © pyridine and especially pyridine amines amines ¢ tetrahydrfuran tetramethylethylenediamine tetramethylethylenediamine bipyridine piperidine dienes and dienes » olefins olefins » triethylamine ethylenediamine Ely » (TMEDA ), and complex compounds include carbon atoms associated with it from to 46 carbon atoms last oxidation over those in which the metal is in the oxidation state X on the original 0 + groups and the preferred coordination complex compounds According to this invention are complex compounds symmetrical: of the formula x" 15 volts and ha is the groups of ©; Each individually is RY SRY, RS RY where vo to 88 non-hydrogen atoms is 1 hydrogen; or a group having a hydrocarbyl, a hydrocarbyl halo-substituted, a hydrocarbyl-substituted hydrocarbyloxy, a hydrocarbyl-substituted hydrocarbyl-amino, a hydrocarbyl silyl, or optionally a hydrocarbyl silyl group substituted by one or more of the RE and 18, RS, RY hydrocarbyl groups; and each of which, at each occurrence of it separately, is a hydrocarbyloxy, hydrocarbyl _, hydrocarbyl gud siloxy, or hydrocarbyl silylamino ; Di(hydrocarbylsilyl) amino or di(hydrocarbyl amino) or di(hydrocarbyl)phospheno or hydrocarbyl sulfido hydrocarbyl or halo-substituted or hydrocarbyl-substituted hydrocarbyloxy or hydrocarbyl

VY

substituted with a hydrocarbyl amino or hydrocarbyl silyl or hydrocarbyl silyl hydrocarbyl having a 71 to 1 non-overlapping do gana non-hydrogen atom; or 01 to 1 conjugated 5 RA, 185, RS RY, RY hydrogen ; or optionally two or more are covalently joined together to form one or more combined rings or ring systems that; and have one or more R to 88 non-hydrogen atoms per group 1 of 0

Yo to 1 fused single rings or unsubstituted or substituted ring systems of non-hydrogen atom. 01 to 1 non-hydrogen atom; or a non-overlapping group of is a hydrocarbyl or RP and the preferred groups are those in which a hydrocarbyl substituted for a hydrocarbyloxy or a hydrocarbyl substituted for a hydrocarbyl amino; is T and 0 is a hydrocarbyl or hydrocarbylsilyl and 7 is a ©0 or 17 ; groups are a hydrocarbyl or hydrocarbylsilyl and the most preferred RE is one in which 1 is the containing 1. On the atom that differs from the favorite at position 7 of M©, we find that (Jad) and is or propoxy or ethoxy or methoxy is methoxy (RP); -7 in which vo is 1,1- second Methylamino 1-10 or methylethyloxy or propoxy methylethylamino ¢ diethylamino sid diethylamino or dipropylamino dipropylamino » methylphenylamino methyl ethylamine » or dipropylamino or propylamino dibutylamino butylamino or morpholinyl or piperidinyl or piperidinyl dibutylamino 00 © hexahydro-1H-azepin-1-yl yl-1- or hexahydro-111- pyrrolidinyl-eupene -1- or octahydro-111-ontine hexahydro-1(2H)-azocinyl hexahydroocinyl octahydro-1(2H)- or octahydro-211(1)- Oocinyl octahydro-1H-azonin-1-yl yl (RP) —T and from the most preferred group are those with the . azecinyl or piperidinyl methylphenylamino sud or methylphenyl dimethylamino for methyl amino Yo .pyrrolidinyl df piperidinyl p

V¢ In another aspect of this invention, any of the ligand or complex metal compound has one or more incorporating rings or ring systems in addition to C or adenyl. The combined rings or ring systems contain one or more Cua indenyl atoms. The offense being 17 or 0< and 17 being much more preferred : the other highly complex compounds correspond to the formula ° —~ i } ss : where the symbols are defined as above; or more preferable; The formula corresponds to “oF sat” where the symbols are recognized as above, and the highly preferred compounds are complex metals compounds 1 le Z- and ligands thereof containing an offending atom, where the metals complexes are -0-; Y M and 7 are related to Cp of 7-*2- ; and *2 is associated with or SiR%,SiR*, or CR*; J stands for Z* ; and is -PR*- » -NR*- » -S- or SiR,CR*;SiR*;, Ar CR%,SiR*,CR J CR,*SiR*, J CR*, = CR *, AR CR*,CR*;

m GeRy* J CR¥,CR¥,CR*, J CR¥,CR*,SiR*;¢ and R® separately at each occurrence of not a hydrogen J of the selected hydrocarbyl member; hydrocarpyloxi, silyl, halogenated alkyl, or halogenated aryl; and unions thereof; And *8 has a number of up to 01 atoms

F

Vo (other than hydrogen); or RF (where Z is of non-hydrogen RY; optionally two groups of 7 form a ring system; R* of 7 and group R* of the original 4+ oxidation state AM is ¥ and is equal to zero; P where or trimethyl benzyl or benzyl methyl; and 7 separately when each occurrence is a methyl

X or two groups pyrollyl and pyrryl allyl and allyl trimethylsilylmethyl silylmethyl © yl B= = or 7-butene 14-butane-diyl butane-diyl 4-1 together is 4-6 2,3-dimethyl-2-butene Y= or 7 7-dimethyl-7-butene 2-butene-1,4-diyl 4-diyl and 4-bisyl 2-methyl- 2-butene-1 Y= and 7- methyl -7- butene 4-diyl diyl 0 xylyldiyl osylidyl metal complexe Also, it is highly preferred to find complex metal compounds 7-01*- of which containing the offending atoms, where = 2- is ligands and ligands - is -0- + -8-; Y and M is; *2 is associated with m© and 7 is associated with 7

CR*;CR*, or SiR*,SiR*; 4 CRy* J is *Z * ; and is -PR*- ¢« NR*- or SiR,CR*;SiR*, JfCR%;SiR*,CR J CR,*SiR*, J CR*, = or wy; and GeR* Jl CR¥,CR*,CR*; R CR¥,CR*,SiR*; d separately when each occurrence is a hydrogen or a selected member of * hydrocarbyl ; hydrocarpyloxy, silyl, alkyl halogenated, or aryl halogenated; and unions including atoms other than hydrogen; Optionally two groups 01 are formed; And the *8 mentioned in it is even

Y of 7 and group *18 of R* other than hydrogen); or combination R* of 2 (where RH is a ring system; 7 + the original oxidation oxidation of Ala equals zero; 14 in q 1 is P where the -2 allyl) N,N-dimethylaminomethyl)phenyl i.e. 2-(N,N-dimethyl)aminobenzyl (trimethylsilylallyl) or trimethylsilylallyl or methylallyl and metal complexe ligands are also highly preferred complex metal compounds 2* from 7-*2- ; and ble -7- are compounds containing opposite atoms where Yo ligands

¢ -PR*- ¢ -NR*- ¢ -8- « —0- and 7 is M bonded and 7 is Cp bonded to

CR*, = CR*, R CR*,CR*, J SiR*;SiR*;, J CRy* J SiRp* is Z* and is OR CR%CR*SiR*, J SiR,CR*SiR*, J CR%SiR%,CR J CR,*SiR*, any; and GeR*, CR¥,CR*,CR*, M*8 separately when each occurrence is a hydrogen or a selected hydrocarbyl member; hydrocarpyloxy, silyl, alkyl halogenated, or aryl halogenated; and federations thereof; The mentioned *8 has up to 10 non-hydrogen atoms; Optionally form two groups R* of Z (where R* is non-hydrogen); or R* of 7 and R* of 7 group ring system;

Xoo 7+; 14 in the original oxidation state 1 is zero; is equal to P where 10 -1 ¢ 3-butadiene Y = 0-butadiene; hexadiene or 7 ; Desirably a metal from one of the groups? to +4 _ for the elements lanthanates or actendides; which is in the original oxidation state +7 2 +9 or 1 and is . 17; more desirable a metal of one of Groups 9 to - the metallic complex compounds subject of the invention which have somewhat different properties or 9-17; One of the groups =F is a metal from one of the groups M, the one in it is a metal selected from M, and it is preferable that the one in it has . 01-17 one of the groups. They are the most detailed Zn 77 and the “HE” or “Zn” Ti group is not desirable © is the most highly favored metal; Especially for use in complex compounds, Ti, and it is the ligand containing a Cp atom that contains only one ligand that contains Zr, in violation of the subject matter of this invention; While the complex compounds that contain ligands are M©; which is at least one of them. It is a ligand containing a Yo atom

For in one embodiment it is preferably 11 in the original oxidation Als +4 ; while ; Alternatively it is preferred that 11 is in the original + oxidation state; It is most preferred to be 121 in the original +7 oxidation state. In another aspect of the invention 577 is preferred to be NR * - ; It would be more preferable to 0 to be—NR* those in which *8 is a group with a primary or secondary carbon atom -bonded to 17 . It is more preferable that the R * be a cyclohexyl or isopropyl . There is a coordinate complex 00 i / . m 4 iL Na, : It includes the illustrative derivatives of the metals that may be used when conducting This invention contains 1 (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-n)-3-(1-pyrrolidinyl)-1H-inden - 1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-n)-2- methyl-3-(1 -pyrrolidinyl)- 1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1, 2,3,3a,7a-n)-2ethyl-3-(1-pyrrolidinyl)- Vo 1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)- 1,1-dimethyl-1-((1,2,3,3a,7a-1)-2-ethyl-6-methyl-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2 -)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-n)-4-methyl-3-(1-pyrrolidinyl) )- 1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium Ye. (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-1))-5-ethyl-3-(1-pyrrolidinyl)- 1H-inden -1-yl)silanaminato(2-)-N)dimethyltitanium

YQ.

Ya

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-1)-6-(1-methylethyl)-3-(1- pyrrolidinyl)- 1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-1) -5-ethyl-6-methyl-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl -1-((1,2,3,3a,7a-n)-5-butyl-3-(1-pyrrolidinyl)-°1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N -(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-1)-5-(1,1-dimethylethyl)-3-(1- pyrrolidinyl)- 1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-1) -5-phenyl-3-(1-pyrrolidinyl)- 1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium 01 (N-(1,1-dimethylethyl)-1,1-dimethyl-1- ((1,2,3,3a,7a-1)-3-(1-pyrrolidinyl)-1H-inden- 1-yl)silanaminato(2-)-N)((1,2,3,4-n )-1,3-pentadiene)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-17)-2-methyl-3(1) -pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)((1,2,3,4-11)-1,3-pentadiene)titanium (N-(1,1-dimethylethyl) -1,1-dimethyl-1-((1,2,3,3a,7a-1))-2-ethyl-3-(1-pyrrolidinyl)- Vo 1H-inden-1-yl)silanaminato(2- )-N)((1,2,3,4-n)-1,3-pentadiene)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3) ,3a,7a-n)-4-methyl-3-(1-pyrrolidinyl)- 1H-inden-1-yl)silanaminato(2-)-N)((1,2,3,4-11)-1 ,3-pentadiene)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((12,3,3a,7a-n)-5-ethyl-3-(1-pyrrolidinyl)- 1H-inden-1-yl)silanaminato(2-)-N)((1,2,3,4-n)-1,3-pentadiene)titanium Y. (N-(1,1-dimethylethyl)-1 ,1-dimethyl-1-((1,2,3,3a,7a-n)-6-(1-methylethyl)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2- )-N)((1,2,3,4-n)-1,3-pentadiene)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1+((1,2,3) ,3a,7a-1)-5-ethyl-6-methyl-3-(1- pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)((1,2,3,4- n)-1,3-pentadiene)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-n)-5-butyl-3- (1-pyrrolidinyl)-Yo 1H-inden-1-yl)silanaminato(2-)-N)((1,2,3,4-n)-1,3-pentadiene)titanium (N-(1,1) -dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-5-(1,1-dimethylethyl)-3-(1-pyrrolidinyl)-1H-inden-1 -yl)silanaminato(2-)-N)((1,2,3,4-?)-1,3-pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-5-phenyl-3-(1-pyrrolidinyl)-1H-inden- 1-yl)silanaminato(2-)-N)((1,2,3,4-?)-1,3-pentadiene)titanium ((2-(dimethylamino)phenyl)methyl}(N-(1,1 -dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-7)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N )titanium ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1- ° ((1,2,3,3a,7a-7)-2- methyl-3-(1-pyrrolidinyl)-1H-inden- 1 -yl)silanaminato(2-)-

N)titanium ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1- ((1,2,3,3a,7a-7)-2- ethyl-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-

N)titanium 1 ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1- (1,2,3,3a,7a-?)-2- ethyl-6-methyl-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-

N)titanium ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1- ((1,2,3,3a,7a-7)-4- methyl-3-(1-pyrrolidinyl)-1,1-inden-1-yl)silanaminato(2-)- \o

N)dimethyltitanium ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1- ((1,2,3,3a,7a-?)-5ethyl- 3-(1-pyrrolidinyl)-1H-inden- 1-yl)silanaminato(2-)-

Ntitanium ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1- Y. ((1,2,3,3a,7-2)-6- (1-methylethyl)-3-(1-pyrrolidinyl)-1H-inden- 1-yl)silanaminato(2-)-

N)titanium ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1- (1,2,3,3a,7a-?)-5-ethyl -6-methyl-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-

N)titanium Yo ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1- ((1,2,3,3a,7a-7)-5 -butyl-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-

N) titanium

1 ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1, ,3,3a,7a-7)-5-(1, 1-dimethylethyl)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2- )-N)titanium ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl) )-1,1-dimethyl-1-((1, ,3,3a,7a-?)-5-phenyl-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)- N)titanium ° (N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-?)-2-methyl-3-(1-pyrrolidinyl)-1H-inden-1- yl)silanaminato(2-)-N)dimethyltitanium (N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-?)-2-ethyl-3-(1-pyrrolidinyl) -1H-inden- 1-yl)silanaminato(2-)-N)dimethyltitanium (N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-?)-2-ethyl- 6-methyl-3-(1-pyrrolidinyl)-01 1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-cyclohexyl-1,1-dimethyl-1-((1,2,3) ,3a,7a-?)-4-methyl-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-cyclohexyl-1,1-dimethyl-1- ((1,2,3,3a,7a-?)-5-ethyl-3-(1-pyrrolidinyl)-1H-inden- 1-yl)silanaminato(2-)-N)dimethyltitanium Vo (N-cyclohexyl- 1,1-dimethyl-1-((1.2,3,3a,7a-?)-6-(1-methylethyl)-3-(1-pyrrolidinyl)- 1H-inden-1-yl)silanaminato(2-) -N)dimethyltitanium (N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-?)-5-ethyl-6-methyl-3-(1-pyrrolidinyl)- 1H- inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-?)-5-butyl-3-( 1-pyrrolidinyl)-1H-inden-Y. 1-yl)silanaminato(2-)-N)dimethyltitanium

(N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-?)-5-(1,1-dimethylethyl)-3-(1-pyrrolidinyl)-1H-inden- 1-yl)silanaminato(2-)-N)dimethyltitanium (N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-?)-5-phenyl-3-(1- pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium Yo (1,1-dimethyl-N-(1-methylethyl)-1-((1,2,3,3a,7a- ?)-3-(1-pyrrolidinyl)-1H-inden-1- yl)silanaminato(2-)-N)dimethyltitanium (1,1-dimethyl-N-(1-methylethyl)-1-((1,2) ,3,3a,7a-?)-2-methyl-3-(1-pyrrolidinyl)-1H-

1 inden-1-yl)silanaminato(2-)-N)dimethyltitanium (1,1-dimethyl-N-(1-methylethyl)-1-((1,2,3,3a,7a-?)-2- ethyl-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (1,1-dimethyl-N-(1-methylethyl)-1-((1,2, 3,3a,7a-?)-2-ethyl-6-methyl-3-(1- pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium ° (1,1-dimethyl- N-(1-methylethyl)-1-((1,2,3,3a,7a-?)-4-methyl-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2- )-N)dimethyltitanium (1,1-dimethyl-N-(1-methylethyl)-1-((1,2,3,3a,7a-?)-5-ethyl-3-(1-pyrrolidinyl)-1H - inden-1-yl)silanaminato(2-)-N)dimethyltitanium (1,1-dimethyl-N-(1-methylethyl)-1-((1,2,3,3a,7a-?)-6- (1-methylethyl)-3-(1- 01 pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (1,1-dimethyl-N-(1-methylethyl)-1-( (1,2,3,3a,7a-?)-5-ethyl-6-methyl-3-(1- pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (1, 1-dimethyl-N-(1-methylethyl)-1-((1,2,3,3a,7a-?)-5-butyl-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato (2-)-N)dimethyltitanium 1

(1,1-dimethyl-N-(1-methylethyl)-1-((1,2,3,3a,7a-?)-5-(1,1-dimethylethyl)-3-(1- pyrrolidinyl)- 1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (1,1-dimethyl-N-(1-methylethyl)-1-((1,2,3,3a,7a-?)-5 -phenyl-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (1,1-dimethyl-N-(phenylmethyl)-1-((1,2,3) ,3a,7a-?))-3-(1-pyrrolidinyl)-1H-inden-1- Y.yl)silanaminato(2-)-N)dimethyltitanium (1,1-dimethyl-N-(phenylmethyl)-1 -((1,2,3,3a,7a-?)-2-methyl-3-(1-pyrrolidinyl)-1H- inden-1-yl)silanaminato(2-)-N)dimethyltitanium (1,1- dimethyl-N-(phenylmethyl)-1-((1,2,3,3a,7a-?)-2-ethyl-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-) -N)dimethyltitanium Yo (1,1-dimethyl-N-(phenylmethyl)-1-((1,2,3,3a,7a-?)-2-ethyl-6-methyl-3-(1- pyrrolidinyl) -1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (1,1-dimethyl-N-(phenylmethyl)-1-((1,2,3,3a,7a-?)-4- methyl-3-(1-pyrrolidinyl)-1H-

YY inden-1-yl)silanaminato(2-)-N)dimethyltitanium (1,1-dimethyl-N-(phenylmethyl)-1-((1,2,3,3a,7a-?)-5-ethyl- 3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (1,1-dimethyl-N-(phenylmethyl)-1-((1,2,3,3a, 7a-?)-6-(1-methylethyl)-3-(1- pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium ° (1,1-dimethyl-N-(phenylmethyl) )-1-((1,2,3,3a,7a-?)-5-ethyl-6-methyl-3-(-1- pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)- N)dimethyltitanium (1,1-dimethyl-N-(phenylmethyl)-1-((1,2,3,3a,7a-?)-5-butyl-3-(1-pyrrolidinyl)-1H- inden-1 -yl)silanaminato(2-)-N)dimethyltitanium (1,1-dimethyl-N-(phenylmethyl)-1-((1,2,3,3a,7a-?)-5-(1,1-dimethylethyl) )-3-(1- 01 pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (1,1-dimethyl-N-(phenylmethyl)-1-((1,2,3) ,3a,7a-?)-5-phenyl-3-(1-pyrrolidinyl)-1H- inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1, 1-dimethyl-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium \o (N -methyl-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N) dimethyltitanium (N-ethyl-1,1-dimethyl-1-((1,2,3,3a,7a-7)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-) -N)dimethyltitanium (N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1- Y.yl) silanaminato(2-)-N)dimethyltitanium (1,1-dimethyl-N-phenyl-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1 - yl)silanaminato(2-)-N)dimethyltitanium (1,1-dimethyl-N-(methylphenyl)-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)- 1H-inden-1- yl)silanaminato(2-)-N)dimethyltitanium Yo (N-cyclododecyl-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(1 -pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-1,1-dimethyl-N-(1-methylethyl)-1-((1,2,3,3a, 7a-?)-3-(1-pyrrolidinyl)-1H-inden-

vy

1-yl)silanaminato(2-)-N)dimethyltitanium (N-butyl-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H -inden-1- yl)silanaminato(2-)-N)dimethyltitanium (1,1-dimethyl-N-propyl-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl) )-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium ° (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a) -?)-3-(1-pyrrolidinyl)-1H-inden- 1-yl)silanaminato(2-)-N)((1,2,3,4-?)-1,3-pentadiene)titanium (N -methyl-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N) ((1,2,3,4-7)-1,3-pentadiene)titanium (N-ethyl-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3 (1-pyrrolidinyl)-1H-inden-1- 01a yl)silanaminato(2-)-N)((1,2,3,4-?)-1,3-pentadiene)titanium (N -cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1- yl)silanaminato(2-)-N )((1,2,3,4-?)-1,3-pentadiene)titanium ‎(1,1-dimethyl-N-phenyl-1-((1,2,3,3a,7a-?)- 3-(1-pyrrolidinyl)-1H-inden-1- \o yl)silanaminato(2-)-N)((1,2,3,4-?)-1,3-pentadiene)titanium (1,1) -dimethyl-N-(methylphenyl)-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N) ((1,2,3,4-7)-1,3-pentadiene)titanium (N-cyclododecyl-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3 (1-pyrrolidinyl)-1H-inden-1- yl)silanaminato(2-)-N)((1,2,3,4-?)-1,3-pentadiene)titanium Y. (N-1,1 -dimethyl-N-(1-methylethyl)-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)- 1H-inden- 1-yl)silanaminato(2-)- N)((1,2,3,4-?)-1,3-pentadiene)titanium (N-butyl-1,1-dimethyl-1-((1,2,3,3a,7a-?)- 3-(1-pyrrolidinyl)-1H-inden-1- yl)silanaminato(2-)-N)((1,2,3,4-7)-1,3-pentadiene)titanium (1,1-dimethyl) -N-propyl-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1- Yo yl)silanaminato(2-)-N)((1 ,2,3,4-?)-1,3-pentadiene)titanium ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1- ((1 ,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)titanium

'ya.

P ((2-(dimethylamino)phenyl)methyl)(N-methyl-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(1- pyrrolidinyl) -1H-inden-1-yl)silanaminato(2-)-N)titanium ((2-(dimethylamino)phenyl)methyl)(N-ethyl-1,1-dimethyl-1-((1,2, 3,3a,7a-?)-3-(1- pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)titanium ((2-(dimethylamino)phenyl)methyl)( N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-7)- ° 3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2- )-N)titanium ((2-(dimethylamino)phenyl)methyl)(1,1-dimethyl-N-phenyl-1-((1,2,3,3a,7a-?)-3~(1 - pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)titanium ((2-(dimethylamino)phenyl)methyl)(1,1-dimethyl-N-(methylphenyl)-1 -((1,2,3,3a,7a-7)-3- (1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)titanium 01

((2-(dimethylamino)phenyl)methyl)(N-cyclododecyl-1,1-dimethyl-1-((1,2,3,3a,7a- 7)-3-(1-pyrrolidinyl)-1H-inden -1-yl)silanaminato(2-)-N)dimethyltitanium ((2-(dimethylamino)phenyl)methyl)(N-1,1-dimethyl-N-(1-methylethyl)-1- ((1,2, 3,3a,7a-7)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)titanium ((2-(dimethylamino)phenyl)methyl)(N-butyl- 1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(1- Vo pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)titanium ( (2-(dimethylamino)phenyl)methyl)(1,1-dimethyl-N-propyl-1-((1,2,3,3a,7a-7)-3-(1-pyrrolidinyl)-1H-inden- 1-yl)silanaminato(2-)-N)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-( 1-pyrrolidinyl)-1H-inden- 1-yl)silanaminato(2-)-N)dimethyltitanium XY. (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(1-piperidinyl)-1H-inden- 1-yl) silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(hexahydro-1H- azepin-1-yl)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3) ,3a,7a-?)-3-(hexahydro-1(2H)- Yo azocinyl)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)- 1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(octahydro-1H-azonin-1-yl)dimethyltitanium

Yo (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,72-?)-3 -(octahydro-1(2H)- azecinyl)-1H- inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3 -(dimethylamino)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a) ,7a-7)-3-(diethylamino)-1 H-inden- ° 1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1- ((1,2,3,3a,7a-2)-3 -(dipropylamino)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(dibutylamino)-1H-inden- 1-yl)silanaminato (2-)-N)dimethyltitanium 01 (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-7)-3 -(ethylmethylamino)-1H - inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)- 3 -(methylphenylamino)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1(1,2,3,3a, 7a-?)-3-(methyl(phenylme \o thyl)amino)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1- dimethyl-1-((1,2,3,3a,7a-7)-3-((;1 -dimethyle thyl)methylamino)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium ( N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-7)-3-(methyl(1 -meth ylethyl)amino)-1H-inden- 1-yl)silanaminato(2-)-N)dimethyltitanium Y. (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3 -(diphenylpho sphino)-1H-inden-1-yl)silanaminato(2-)-N)dimethyititanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3, 3a,72-?)-3 -(dimethylphosphino)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-( (1,2,3,3a,7a-?)-3 -(methylphenylphosphino)- ~~ Ye 1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl) -1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(diethylphosphino)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(bis(1-methyle thyl)phosphino)-1H-inden -1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3- methoxy-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a- ?)-3-ethoxy-1H-inden-1-°yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2, 3,3a,7a-?)-3-propoxy-1H-inden-1- yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-( (1,2,3,3a,7a-?)-3-butoxy-1H-inden-1- yl)silanaminato(2-)-N)dimethyltitanium 01 (N-(1,1-dimethylethyl)-1,1 -dimethyl-1-((1,2,3,3a,7a-?)-3-((1,1 -dimethylethyl)oxy)- 1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(trimethylsiloxy)-1H-inden-1-yl)silanaminato( 2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(((1,1- dimethy \o lethyl)dimethylsilyl)oxy)-1H-inden--yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2) ,3,3a,7a-?)-3-(1-methylethoxy)-1H- inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1- dimethyl-1-((1,2,3,3a,7a-?)-3-phenoxy-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium Y.

N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(phenylthio)-1il-inden-1-yl)silanaminato(2 -)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(methylthio)-1H-inden- 1- yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-( 1-pyrrolidinyl)-1H-inden-00 1-yl)silanaminato(2-)-N)((1,2,3,4-?)-1,3-pentadiene)titanium (N-(1,1-) dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(1-piperidinyl)-1H-inden- 1-yl)silanaminato(2-)-N) ((1,2,3,4-7)-1,3-pentadiene)titanium

For (N-(1,1-dimethylethyl1)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(hexahydro-1H-azepin-1-yl) )-1H-inden-1-yl)silanaminato(2-)-N)((1,2,3,4-71)-1,3-pentadiene)titanium (N-(1,1-dimethylethyl) -1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(hexahydro-1(2H)- azocinyl)-1H-inden-1-yl)silanaminato(2 -)-N)((1,2,3,4-?)-1,3-pentadiene)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1, 2,3,3a,7a-?)-3-(octahydro-1H-azonin-1- ° y1)((1,2,3,4-?7)-1,3-pentadiene)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(octahydro-1(2H)- azecinyl)-1H -inden-1-yl)silanaminato(2-)-N)((1,2,3,4-?)-1,3-pentadiene)titanium (N-(1,1-dimethylethyl)-1, 1-dimethyl-1-((1,2,3,3a,7a-?)-3-(dimethylamino)-1H- inden-1-yl)silanaminato(2-)-N)((1,2 ,3,4-?)-1,3-pentadiene)titanium 1 (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-? )-3-(diethylamino)-1H-inden- 1-yl)silanaminato(2-)-N)((1,2,3,4-7)-1,3-pentadiene)titanium (N -(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(dipropylamino)-1H- inden-1-yl)silanaminato( 2-)-N)((1,2,3,4-?)-1,3-pentadiene)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1 ,2,3,3a,7a-?)-3-(dibutylamino)-1H-inden- Vo 1-yl)silanaminato(2-)-N)((1,2,3,4-7)- 1,3-pentadiene)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(ethylmethylamino)-1H - inden-1-yl)silanaminato(2-)-N)((1,2,3,4-?)-1,3-pentadiene)titanium (N-(1,1-dimethylethyl)- 1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(methylphenylamino)-1H- inden-1-yl)silanaminato(2-)-N)((1 ,2,3,4-?)-1,3-pentadiene)titanium Y. (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a, 7a-?)-3-(methyl (phenyl methyl)amino)-1H-inden-1-yl)silanaminato(2-)-N)((1,2,3,4-?)-1,3 -pentadiene)titanium : (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-((1, 1 -dimethyl ethyl)methylamino)-1H-inden-1-yl)silanaminato(2-)-N)((1,2,3,4-?)-1,3-pe Yo ntadiene)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(methyl(1-meth ylethyl)amino) -1H-inden-1-yl)silanaminato(2-)-N)((1,2,3,4-?)-1,3-pentad

YA iene)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(diphenylphosphino)-1H-inden-1- yl)silanaminato(2-)-N)((1,2,3,4-?)-1,3-pentadiene)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-( 1,2,3,3a,7a-?)-3-(dimethylphosphino)-1H-inden-1-yl)silanaminato(2-)-N)((1,2,3,4-?)-1, 3-pentadiene)titanium ° (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(methylphenylphosphino)-1H-inden- 1-yl)silanaminato(2-)-N)((1,2,3,4-7)-1,3-pentadiene)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1 -((1,2,3,3a,7a-?)-3-(diethylphosphino)-1H- inden-1-yl)silanaminato(2-)-N)((1,2,3,4-?) -1,3-pentadiene)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(bis(1-methyle) 1 thyl)phosphino)-1H-inden-1-yl)silanaminato(2-)-N)((1,2,3,4-?)-1,3-penta diene)titanium (N-(1,1) -dimethylethyl)-1-dimethyl-1-((1,2,3,3a,7a-?)-3-methoxy-1H-inden-1- yl)silanaminato(2-)-N)((1,2 ,3,4-?)-1,3-pentadiene)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3 -ethoxy-1H-inden-1-Voyl)silanaminato(2-)-N)((1,2,3,4-?)-1,3-pentadiene)titanium (N-(1,1-dimethylethyl) -1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-propoxy-1H-inden-1- yl)silanaminato(2-)-N)((1,2, 3,4-7)-1,3-pentadiene)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3 butoxy-1H-inden-1-yl)silanaminato(2-)-N)((1,2,3,4-?)-1,3-pentadiene)titanium Y. (N-(1,1-dimethylethyl) -1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-((1,1 -dimethylethyl)oxy)- 1H-inden-1-yl)silanaminato(2-) -N)((1,2,3,4-?)-1,3-pentadiene)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3, 3a,7a-?)-3-(trimethylsiloxy)-1H-inden-1-yl)silanaminato(2-)-N)((1,2,3,4-?)-1,3-pentadiene)titanium ( N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-.1)-3-(((1,1- Yo dimethylethyl)dimethylsilyl)oxy) -1H-inden-1-yl)silanaminato(2-)-N)((1,2,3,4-7)- 1,3-pentadiene)titanium (N-(1,1-dimethylethyl)-1, 1-dimethyl-1-((1,2,3,3a,7a-?)-3-(1-methylethoxy)-1H-FD

Ya inden-1-yl)silanaminato(2-)-N)((1,2,3,4-?)-1,3-pentadiene)titanium (N-(1,1-dimethylethyl)-1,1- dimethyl-1-((1,2,3,3a,7a-?)-3-phenoxy-1H-inden-1- yl)silanaminato(2-)-N)((1,2,3,4-? )-1,3-pentadiene)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?))-3-(phenylthio)- 1H-inden-1-yl)silanaminato(2-)-N)((1,2,3,4-?)-1,3-pentadiene)titanium ° (N-(1,1-dimethylethyl)-1, 1-dimethyl-1-((1,2,3,3a,7a-?)-3-(methylthio)-1H-inden-1- yDsilanaminato(2-)-N)((1,2,3,4 -?)-1,3-pentadiene)titanium ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1, »3,3a, 7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)titanium ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl) )-1,1-dimethyl-1-((1, 01 »3,3a,7a-?)-3-(1-piperidinyl)-1H-inden-1-yl)silanaminato(2-)-N)titanium ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1- ((1,2,3,3a,7a-?)-3-(hexahydro- 1H-azepin-1-yl)-1H-inden-1-yl)silanaminato(2-)-

N)titanium ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1- \o ((1,2,3,3a,7a-7)- 3-(hexahydro-1(2H)-azocinyl)-1H-inden-1-yl)silanaminato(2-)-

N)titanium ((2-(dimethylamino)phenyl)methyl)(N~(1,1-dimethylethyl)-1,1-dimethyl-1- ((1,2,3,3a,7a-7)-3- (octahydro-1H-azonin-1-yl)titanium ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1- Y. ((1,2, 3,3a,7a-7)-3-(octahydro-(2H)-azecinyl)-1H-inden-1-yl)silanaminato(2-)-

N)titanium ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1- ((1,2,3,3a,7a-?)-3- (dimethylamino)-1H-inden-1-yl)silanaminato(2-)-

N)dimethyltitanium Yo (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-? )-3-(diethylamino)-1H-inden-1- yl)silanaminato(2-)-N)dimethyltitanium

Ye (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(dipropylamino)-1H-inden-1-yl)silanaminato (2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(dibutylamino)-1H- inden- 1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3 -(ethylmethylamino)-1H-° inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3, 3a,7a-?)-3-(methylphenylamino)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-( (1,2,3,3a,7a-?)-3-(methyl (phenyl methyl)amino)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium 01 (N-(1,1 -dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-((1,1-dimethyl ethyl)methylamino)-1H-inden-1-yl)silanaminato (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(methyl(1-meth ylethyl)amino)-1H-inden -1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?))-3 -(diphenylphosphino)-1H- \o inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3) ,3a,7a-?)-3-(dimethylphosphino)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1( 1,2,3,3a,7a-2)-3 -(methylphenylphosphino)- 1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium Y- (N-(1,1,-dimethylethyl)- 1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(diethylphosphino)-1H- inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-( 1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(bis(1-methyle thyl)phosphino)-1H-inden-1-yl )silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-methoxy-1H- inden-1- Yo yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)- 3-ethoxy-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium

Text (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-propoxy-1H-inden-1-yl) silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-butoxy-1H -inden-1- yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a) -?)-3-((1,1-dimethylethylJoxy)- ° 1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1, 1-dimethyl-1-((1,2,3,3a,7a-?)-3-(trimethylsiloxy)-1H- inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N -(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(((1,1-dimethy lethyl)dimethylsilyl)oxy) -1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium 01 (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a, 7a-?)-3-(1-methylethoxy)-1H- ‎inden-1-yl)silanaminato(2-)-N)dimethyltitanium ((2-(dimethylamino)phenyl)methyl)(N-(1 ,1-dimethylethyl)-1,1-dimethyl-1-((1, ,3,3a,7a-?7)-3-phenoxy-1H-inden-1-yl)silanaminato(2-)-N )titanium ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1- Vo ((1,2,3,3a,7a-? )-3-(phenylthio)-1H-inden-1-yl)silanaminato(2-)-N)titanium ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-1 ,1-dimethyl-1- ((1,2,3,3a,7a-?)-3-(methylthio)-1H-inden-1-yl)silanaminato(2-)-N)titanium ( N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden- 1-yl )silanaminato(2-)-N)dimethyltitanium Y. (N-(1-dimethylethyl)-1,1-diphenyl-1-((1,2,3,3a,7a-?)-3-(1) -pyrrolidinyl)-1H-inden-1- yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1-methyl-1-phenyl-1-((1, 2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H- inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl) -1,1-bis(1-methylethoxy)-1-((1,2,3,3a,7a-?))-3-(1- Yo pyrrolidinyl)-1H-inden-1-yl)silanaminato (2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-diethyl-1-((1,2,3,3a,7a-?)-3-(1 -pyrrolidinyl) )-1H-indent- 1-yl)silanaminato(2-)-N)dimethyltitanium

YY

(N-(1,1-dimethylethyl)-1,1-dimethoxy-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl) silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1-ethoxy-1-methyl-1-((1,2,3,3a,7a-?)-3-(1- pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a) -?)-3-(1-pyrrolidinyl)-1H-inden-© 1-yl)silanaminato(2-)-N)((1,2,3,4-?)-1,3-pentadiene)titanium ( N-(1,1-dimethylethyl)-1,1-diphenyl-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden- 1-yl)silanaminato (2-)-N)((1,2,3,4r)-1,3-pentadiene)titanium (N-(1,1-dimethylethyl)-1-methyl-1-phenyl-1-((1, 2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)((1,2,3,4-?)-1, 3-pentadiene)titanium Ve (N-(1,1-dimethylethyl)-1,1-bis(1-methylethoxy)-1-((1,2,3,3a,7a-?)-3-(1- pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)((1,2,3,4-?)-1,3-pentadiene)titanium (N-(1,1-dimethylethyl)- 1,1-diethyl-1-((1,2,3,3a,72a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)((1 ,2,3,4)-1,3-pentadiene)titanium (N-(1,1-dimethylethyl)-1,1-dimethoxy-1-((1,2,3,3a,7a-?)-3 -(1-pyrrolidinyl)-1H- \o inden-1-yl)silanaminato(2-N)((1,2,3,4-?)-1,3-pentadiene)titanium (N-(1,1) -dimethylethyl)-1-ethoxy-1-methyl-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-) -N)((1,2,3,4-?)-1,3-pentadiene)titanium ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-1,1-dimethyl -1-((1, ,3,3a,7a-2)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)titanium Y. ((2-(dimethylamino) )phenyl)methyl)(N-(1,1-dimethylethyl)-1,1-diphenyl-1- ((1,2,3,3a,7a-7)-3-(1-pyrrolidinyl)-1H-inden - 1-yl)silanaminato(2-)-N)titanium ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-1-methyl-1-phenyl-1- ((1, 2,3,3a,7a-7)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)titanium ((2-(dimethylamino)phenyl)methyl)(N- (1,1-dimethylethyl)-1,1-bis(1-methylethoxy)- | Ye 1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)titanium ((2-(dimethylamino) phenyl)methyl)(N-(1,1-dimethylethyl)-1,1-diethyl-1- ((1,2,3,3a,7a-7)-3-(1-pyrrolidinyl)-1H-inden- 1-yl)silanaminato(2-)-N)titanium

YY

((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-1,1-dimethoxy-1- ((1,2,3,3a,7a-?)-3-pyrrolidinyl)- 1H-inden-1-yl)silanaminato(2-)-N)titanium ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-1-ethoxy-1-methyl-1- ( (1,2,3,3a,7a-7)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)titanium (1,1'<(?.sup. 4-1,3-butadiene-1,4-diyl)bis(benzene))(N-(1,1-dimethylethyl)-1,1- ° dimethyl-1-((1,2,3,3a,7a) -?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)t itanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-( (1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden- 1-yl)silanaminato(2-)-N)((1,2,3,4-?) -2,4-hexadiene)titanium ((2-(dimethylamino)methyl)phenyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1- 01 ((1,2,3,3a,7a -?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)titanium dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-( (1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)- 1H-inden-1-yl)silanaminato(2-)-N)titanium (N-(1,1-dimethylethyl)- 1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden- 1-yl)silanaminato(2-)-N)bis(phenylmethyl) )titanium \o (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden- 1-yl)silanaminato(2-)-N)bis(phenylmethyl)bis((trimethylsilyl)methyl)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3) ,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden- 1-yl)silanaminato(2-)-N)bis(phenylmethyl)bis(2,2-dimethylpropyl)titanium (1,1' -(?.sup.4-1,3-butadiene-1,4-diyl)bis(benzene))(N-cyclohexyl-1,1-dimethyl-1- Y. ((1,2,3,3a, 7a-7)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)titanium (N-cyclohexyl-1,1-dimethyl-1-((1,2,3) ,3a,7a-?)-3-(1-pyrrolidinyl)- 1H-inden-1- yl)silanaminato(2-)-N)((1,2,3,4-?)-2,4-hexadiene )titanium ((2-(dimethylamino)methyl)phenyl)(N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-?)- 3-(1-pyrrolidinyl)-1H -inden-1-yl)silanaminato(2-)-N)titanium Yo dichloro(N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(1 -pyrrolidinyl)-1H-inden- 1-yl)silanaminato(2-)-N)titanium (N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3 -(1-pyrrolidinyl)-1H-inden-1-

Ye yl)silanaminato(2-)-N)bis(phenylmethyl)titanium (N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl) )-1H-inden-1- yl)silanaminato(2-)-N)bis(phenylmethyl)bis((trimethylsilyl)methyl)titanium (N-cyclohexyl-1,1-dimethyl-1-((1,2,3) ,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1- yl)silanaminato(2-)-N)bis(phenylmethyl)bis(2,2-dimethylpropyl)titanium ° (1,1 '-(?.sup.4-1,3-butadiene-1,4-diyl)bis(benzene))(N-cyclododecyl-1,1-dimethyl-1- ((1,2,3,3a,7a -?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)titanium (N-cyclododecyl-1,1-dimethyl-1-((1,2,3, 3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1- yDsilanaminato(2-)-N)((1,2,3,4-?)-2,4-hexadiene)titanium ( (2-(dimethylamino)methyl)phenyl)(N-cyclododecyl-1,1-dimethyl-1-((1,2,3,3a,7a- 01 ?)-3-(1-pyrrolidinyl)-1H-inden -1-yl)silanaminato(2-)-N)titanium dichloro(N-cyclododecyl-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl) -1H- inden-1-yl)silanaminato(2-)-N)titanium (N-cyclododecyl-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(1 -pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)bis(phenylmethyl)titanium Vo (N-cyclododecyl-1,1-dimethyl-1-((1,2,3,3a,7a) -?)-3-(1-pyrrolidinyl)-1H-inden-1- yDsilanaminato(2-)-N)bis(phenylmethyl)bis((trimethylsilyl)methyltitanium (N-cyclododecyl-1,1-dimethyl-1-( (1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1- yl)silanaminato(2-)-N)bis(phenylmethyl)bis(2,2-dimethylpropyltitanium ( 1,1'-(4-1,3-butadiene-1,4-diyl)bis(benzene))(N-methyl-1,1-dimethyl-1- Y. ((1,2,3,3a, 7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)titanium (N-methyl-1,1-dimethyl-1-((1,2,3) ,3a,7a-?))-3-(1-pyrrolidinyl)-1H-inden-1-

yDsilanaminato(2-)-N)((1,2,3,4t)-2,4-hexadiene)titanium ((2-(dimethylamino)methyl)phenyl)(N-methyl-1,1-dimethyl-1- ((1,2,3,3a,7a-7)-3-(1- pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)titanium Yo dichloro(N-methyl-1,1 -dimethyl-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)titanium (N-methyl- 1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-

vo yl)silanaminato(2-)-N)bis(phenylmethyl)titanium (N-methyl-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl) )-1H-inden-1- yl)silanaminato(2-)-N)bis(phenylmethyl)bis((trimethylsilyl)methyl)titanium (N-methyl-1,1-dimethyl-1-((1,3,3a) ,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-y

D)silanaminato(2-)-N)bis(phenylmethyl)bis(2,2-dimethylpropyl)titanium ° (1,1'<(?.sup.4-1,3-butadiene-1,4-diyl)bis (benzene))(1,1-dimethyl-N-(phenylmethyl)- 1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl) silanaminato(2-)-N)titanium (1,1-dimethyl-N-(phenylmethyl)-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden -1- yl)silanaminato(2-)-N)((1,2,3,4-7)-2,4-hexadiene)titanium ((2-(dimethylamino)methyl)phenyl)(1,1-dimethyl -N-(phenylmethyl)-1-((1,2,3,3a,7a-1 ?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)titanium dichloro(1,1-dimethyl-N-(phenylmethyl)-1-((1,2,3,3a,7a-,)-3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2 -)-N)titanium (1,1-dimethyl-N-(phenylmethyl)-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1- yl)silanaminato(2-)-N)bis(phenylmethyl)titanium Vo (1,1-dimethyl-N-(phenylmethyl)-1-((1,2,3,3a,7a-?)-3-(1 -pyrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)bis(phenylmethyl)bis((trimethylsilyl)methyl)titanium (1,1-dimethyl-N-(phenylmethyl)-1-((1) ,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1- yDsilanaminato(2-)-N)bis(phenylmethyl)bis(2,2-dimethylpropyl)titanium (1, 1'-(? .sup.4-1,3-butadiene-1,4-diyl)bis(benzene))(1-((1,2,3,3a,7a-?)-3- Y.(dimethylamino)-1H- inden-1-yl)-N-(1,1-dimethylethyl)-1,1- dimethylsilanaminato(2-)-N)titanium (1-((1,2,3,3a,7a-?)-3- (dimethylamino)-1H-inden-1-y1)-N-(1,1-dimethylethyl)-1,1- dimethylsilanaminato(2-)-N)1,2,3,4-?)-2,4- hexadiene)titanium ((2-(dimethylamino)methyl)phenyl)(1-((1,2,3,3a,7a-?)-3-(dimethylamino)-1H- Yo inden-1-yl)-N- (1,1-dimethylethyl)-1,1-dimethylsilanaminato(2-)-N)titanium dichloro(1-((1,2,3,3a,7a-?)-3-(dimethylamino)-1H-inden- 1-y1)-N-(1,1-dim ethylethyl)-1,1-dimethylsilanaminato(2-)-N)titanium

(1-((1,2,3,3a,7a-?)-3-(dimethylamino)-1H-inden-1-yl)-N-(1,1-dimethylethyl)-1,1- dimethylsilanaminato(2 -)-N)bis(phenylmethyl)titanium (1-((1,2,3,3a,7a-?)-3-(dimethylamino)- 1H-inden-1-yl)-N-(1,1- dimethylethyl)-1,1- dimethylsilanaminato(2-)-N)bis(phenylmethyl)bis((trimethylsilyl)methyl)titanium (1-((1,2,3,3a,7a-?)-3-(dimethylamino) -1H-inden-1-yl)-N-(1,1-dimethylethyl)-1,1- ° dimethylsilanaminato(2-)-N)bis(phenylmethyl)bis(2,2-dimethylpropyl)titanium (1,1) ‘«(? .sup.4-1,3-butadiene-1,4-diyl)bis(benzene))(N-(1,1-dimethylethyl)-1,1- dimethyl-1-((1,2 ,3,3a,7a-?)-3~(1 -piperidinyl)-1H-inden-1-yl)silanaminato(2-)-N)ti tanium (N-(1,1-dimethylethyl)-1,1 -dimethyl-1-((1,2,3,3a,7a-?)-3-(1-piperidinyl)-1H-inden- 1 1-yl)silanaminato(2-)-N)((1,2 ,3,4-?)-2,4-hexadiene)titanium ((2-(dimethylamino)methyl)phenyl)}(N-(1,1-dimethylethyl)-1,1-dimethyl1-1- ((1, 2,3,3a,7a-?)-3-(1-piperidinyl)-1H-inden-1-yl)silanaminato(2-)-N)titanium dichloro(N-(1,1-dimethylethyl)-1, 1-dimethyl-1-((,2,3,3a,7a-?)-3-(1-piperidinyl)-1H-inden-1-yl)silanaminato(2-)-N)titanium \o (N- (1,1-methylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(1-piperidinyl)-1H-inden-1-yl)silanaminato(2 -)-N)bis(phenylmethyl)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(1-piperidinyl) )-1H-inden- 1-yl)silanaminato(2-)-N)bis(phenylmethyl)bis((trimethylsilyl)methyl)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-( (1,2,3,3a,7a-?)-3-(1-piperidinyl)- 1H-inden- Y. 1-yl)silanaminato(2-)-N)bis(phenylmethyl)bis(2,2 -dimethylpropyl)titanium (1,1-(?.sup.4-1,3-butadiene-1,4-diyl)bis(benzene))(N-(1,1-dimethylethyl)-1,1- dimethyl- 1-((1,2,3,3a,7a-?)-3-(hexahydro-1H-azepin-1-yl)-1H-inden-1-

yl)silanaminato(2-)-N)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-,)-3-(hexahydro- 1H-azepin-1- Yo yl)-1H-inden-1-yl)silanaminato(2-)-N)((2,3,4-?)-2,4-hexadiene)titanium ((2(dimethylamino) methyl)phenyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,32,7a-2)- 3-(hexahydro-1H-azepin-1-yl) )-1H-inden-1-yl)silanaminato(2-)-N)titanium dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a) -?)-3-(hexahydro-1H-azepin-1-yl)-1H-inden-1-yl)silanaminato(2-)-N)titanium (N-(1,1-dimethylethyl)-1,1- dimethyl-1-((11,23,3a,7a-?)-3-(hexahydro-1H-azepin-1-yl)-1H-inden-1-yl)silanaminato(2-)-N)bis(phenylmethyl) )titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(hexahydro-1H-azepin-1- ° yl) -1H-inden-1-yl)silanaminato(2-)-N)bis(phenylmethyl)bis((trimeth ylsilyl)methyl)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-( (1,2,3,3a,7a-?)-3-(hexahydro-1H-azepin-1- yl)-1H-inden-1-yl)silanaminato(2-)-N)bis(phenylmethyl)bis( 2,2-dime thylpropyl)titanium 1 (1,1'-(?.sup.4-1,3-butadiene- 1,4-diyl)bis(benzene))(N-(1,1-dimethylethyl)- 1,1- dimethyl-1-((1,2,3,3a,7a-?)-3-methoxy-1H-inden-1-yl)silanaminato(2-)-N)titanium (N-(1, 1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-methoxy-1H-inden-1- yl)silanaminato(2-)-N)(( 1,2,3,4-?)-2,4-hexadiene)titanium ((2-(dimethylamino)methyl)phenyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1-(( 1, Ve 2,3,3a,7a-7)-3-methoxy-1H-inden-1-yl)silanaminato(2-)-N)titanium dichloro(N-(1,1-dimethylethyl)-1,1 -dimethyl-1-((1,2,3,3a,7a-?)-3-methoxy-1H-inden-1-yl)silanaminato(2-)-N)titanium (N-(1,1-dimethylethyl) )-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-methoxy-1H-inden-1-

yl)silanaminato(2-)-N)bis(phenylmethyl)titanium Y. (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?) -3-methoxy-1H-inden-1- yl)silanaminato(2-)-N)bis(phenylmethyl)bis((trimethylsilyl)methyl)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl- 1-((1,2,3,3a,7a-?)-3-methoxy-1H-inden-1- yD)silanaminato(2-)-N)bis(phenylmethyl)bis(2,2-dimethylpropyl)titanium (1,1'-(?.sup.4-1,3-butadiene-1,4-diyl)bis(benzene))(N-(1,1-dimethylethyl)-1,1- Yo dimethyl-1- ((1,2,3,3a,7a-?)-3-ethoxy-1H-inden-1-yl)silanaminato(2-)-N)titanium (N-(1,1-dimethylethyl)-1,1 -dimethyl-1-((1,2,3,3a,7a-?)-3-ethoxy-1H-inden-1- yl)silanaminato(2-)-N)((1,2,3,4- ?)-2,4-hexadiene)titanium

Ya

((2-(dimethylamino)methyl)phenyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1- ((1,2,3,3a,7a-?)-3-ethoxy-1H -inden-1-yl)silanaminato(2-)-N)titanium dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?) -3-ethoxy-1H-inden- 1-yl)silanaminato(2-)-N)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a) ,7a-?)-3-ethoxy-1H-inden-1- ° yl)silanaminato(2-)-N)bis(phenylmethyl)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1 -((1,2,3,3a,7a-?-3-ethoxy-1H-inden-1- ylD)silanaminato(2-)-N)bis(phenylmethyl)bis((trimethylsilyl)methyl)titanium (N- (1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-ethoxy-1H-inden-1-yl)silanaminato(2-)-N )bis(phenylmethyl)bis(2,2-dimethylpropyl)titanium 01 (1,1-(? .sup.4-1,3-butadiene-1,4-diyl)bis(benzene))(N-(1, 1-dimethylethyl)-1,1- dimethyl-1-((1,2,3,3a,7a-?)-3-((1,1-dimethylethyl)oxy)-1H-inden-1-yl)silanaminato (2-)-N)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-((1,1- dimethylethyl)oxy)- 1H-inden-1-yl)silanaminato(2-)-N)((1,2,3,4-?)-2,4-hexadiene)titanium \o ((2-(dimethylamino) methyl)phenyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1- ((1,2,3,3a,7a-7)-3-((1,1-dimethylethyl)oxy) -1H-inden-1-yl)silanaminato(2-)-

N)titanium dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-((1,1,1- dimethylethyl) oxy)-1H-inden-1-yl)silanaminato(2-)-N)titanium Y. (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a) ,7a-?)-3-((1,1-dimethylethyl)oxy)- 1H-inden-1-yl)silanaminato(2-)-N)bis(phenylmethyl)titanium (N-(1-dimethylethyl)-1 ,1-dimethyl-1-((1,2,3,3a,7a-?)-3-((1,1-dimethylethyl)oxy)- 1H-inden-1-yl)silanaminato(2-)-

N)bis(phenylmethyl)bis((trimethylsilyl)methyl)titanium Yo (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3 -((1,1-dimethylethyl)oxy)- 1H-inden-1-yl)silanaminato(2-)-N)bis(phenylmethyl)bis(2,2-dimethylpropyl)titanium

Ya (1,1-(?.sup.4-1,3-butadiene-1,4-diyl)bis(benzene))(N-(1,1-dimethylethyl)-1,1- dimethyl-1-( (1,2,3,3a,7a-?)-3-(((1,1-dimethylethyl)dimethylsilyl Joxy)-1H-inden-1- yl)silanaminato(2-)-N)titanium (N-1 ,1-dimethylethyl)-1,1-dimethyl)-1-((1,2,3,3a,7a-?)-3-(((1,1-dimethy lethyl)dimethylsilyl)oxy)-1H-inden -1-yl)silanaminato(2-)-N)((1,2,3,4r7)-2,4- ° hexadiene)titanium ((2-(dimethylamino)methyl)phenyl)(N-(1,1 -dimethylethyl)-1,1-dimethyl-1-((1, 2,3,3a,7a-?)-3-(((1,1-dimethylethyl)dimethylsilylJoxy)-1H-inden-1-yl)si lanaminato(2-)-N)titanium dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(((1 ,1- 1 dimethylethyl)dimethylsilyl)oxy)-1H-inden-1-yl)silanaminato(2-)-N)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((, 2,3,3a,7a-?)-3-(((1,1-dimethyl ethyl)dimethylsilyl)oxy)-1H-inden-1-yl)silanaminato(2-)-N)bis(phenylmethyl) titanium ( N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(((1,1-dimethy lethyl)dimethylsilyl)oxy)- 1H-inden-1-yl)silanaminato(2-)-N)bis(phenyl \o methyl)bis((trimethylsilyl)methyl)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1- ((1,2,3,3a,7a-2)-3-((((1,1 -dimethy lethyl)dimethylsilyl)oxy)-1H-inden-1-yl)silanaminato(2-)-N)bis( phenylmethyl )bis(2,2-dimethylpropyl)titanium (N-(1,1-dimethylethyl)-1-(((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H- inden-1- Y.yl)dimethylsilyl)methanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-(((1,2,3,3a,7a -?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)methyl)silanaminato-(2-)-N-)dimethyltitanium (N-(1,1-dimethylethyl)-2-((1, 2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)-

ethanaminato(2-)-N)dimethyltitanium Yo (N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden- 1-yl)- tetramethylethanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)- 1H-inden-1-yl)-1,1,2,2-

£ tetramethyldisilanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-3-(1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden- 1-yl)-propanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)- 1H-inden-1-y1)- methanaminato(2-)-N)dimethyltitanium ° (N-(1,1-dimethylethyl)-1-((1,2,3,3a,7a-?)-3-( 1-pyrrolidinyl)- 1H-inden-1-yl)- dimethylmethanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3) ,3a,7a-?)-3-methoxy-1H-inden-1-yl)- germanaminato(2-)-N)dimethyltitanium ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl) )-1-(((1,2,3,3a,7a-?)-3-(1- 001 pyrrolidinyl)-1H-inden-1-yl)dimethylsilyl)methanaminato(2-)-N)((1 ,2,3,4-7)-1,3- pentadiene)titanium ((2-(dimethylamino)phenyl)methyl)(N-(1,11lmethylethyi)-1,1-dimethyl-1- (((1, 2,3,3a,7a-7)-3-(1-pyrrolidinyl)-1H-inden-1-yl)methyl)silanaminato-(2-)-N-) ((1,2,3,4-) -1,3-pentadiene)titanium \o ((2-(dimethylamino)phenyl)methyl)(N-(1,1-methylethyl)-2-((1,2,3,3a,7a-?)-3 -(1- pyrrolidinyl)-1H-inden-1-yl)-ethanaminato(2-)-N)((1,2,3,4-?)-1,3- pentadiene)titanium ((2-(dimethylamino) )phenyl)methyl)(N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-?)-3-(1- pyrrolidinyl)-1H-inden-1-yl)- tetramethylethanaminato(2-)-N)((1,2,3,4-?)-1,3- Y.pentadiene)titanium ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl) )-2-((1,2,3,3a,7a-?)-3-(1- pyrrolidinyl)-1H-inden-1-yl)-1,1,2,2-tetramethyldisilanaminato(2-)- N)((1,2,3,4-?)- 1,3-pentadiene)titanium ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-3-((1, 2,3,3a,7a-?)-3-(1- Yo pyrrolidinyl)-1H-inden-1-yl)-propanaminato(2-)-N)((1,2,3,4-?)- 1,3- pentadiene)titanium ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-1-((1,2,3,3a,7a-?)-3-(1 -

pyrrolidinyl)-1H-inden- 1-yl)-methanaminato(2-)-N)((1,2,3,4-7)-1,3-

pentadiene)titanium ((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-1-((1,2,3,3a,7a-?)-3-(1- pyrrolidinyl)- 1H-inden-1-yl)-dimethylmethanaminato(2-)-N)((1,2,3,4-2)-1,3-pentadiene)titanium °

((2-(dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1- ((1,2,3,3a,7a-7)-3-methoxy-1H -inden-1-yl)-germanaminato(2-)-N)((1,2,3,4-?)-1,3- pentadiene)titanium (N-(1,1-dimethylethyl)-1-( ((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1- yl)dimethylsilyl)methanaminato(2-)-N)titanium 01 (N-(1,1 -dimethylethyl)-1,1-dimethyl-1-(((1,2,3,3a,7a-7))-3-(1-pyrrolidinyl)-1H- inden-1-yl)methyl)silanaminato-( 2-)-N-)titanium (N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-7)-3-(1-pyrrolidinyl)-1H-inden-1- y1)-ethanaminato(2-)-N)titanium (N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H- inden-1-yl)- \o tetramethylethanaminato(2-)-N)titanium (N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-7)-3-(1) -pyrrolidinyl)-1H-inden-1-y1)-1,1,2,2- tetramethyldisilanaminato(2-)-N)titanium (N-(1,1-dimethylethyl)-3-((1,2,3) ,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)- propanaminato(2-)-N)titanium Y. (N-(1,1-dimethylethyl)-1-( (1,2,3,3a-?)-3(1-pyrrolidinyl)-1H-inden-1-yl)- methanaminato(2-)-N)titanium (N-(1,1-dimethylethyl)-1 ((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)- dimethylmethanaminato(2-)-N)titanium (N-(1,1-dimethylethyl) )-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-methoxy-1H-inden-1-yl)- Yo germanaminato(2-)-N)titanium (N -(1-dimethylethyl)-1-(((1,2,3,3a,7a-?)-3-methoxy-1H-inden-1-yl)dimeth ylsilyl)methanaminato(2-)-N)dimethyltitanium

1A (N-(1,1-dimethylethyl)-1,1-dimethyl-1-(((1,2,3,3a,7a-?)-3-methoxy-1H-inden-1-yl)methyl) silanaminato-(2-)-N-)dimethyltitanium (N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-?)-3-methoxy-1H-inden-1-yl )-etha naminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-?)-3-methoxy-1H-inden-1- yl)-tetr °amethylethanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-?)-3-methoxy-1H-inden- 1-y1)-1,2,2- tetramethyldisilanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-3-((1,2,3,32,7a-?)-3- methoxy-1H-inden-1-yl)-prop anaminato(2-)-N)dimethyltitanium 01 (N-(1,1-dimethylethyl)-1-((1,2,3,3a,7a-?)- 3-methoxy-1H-inden-1-yl)-meth anaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1-((1,2,3,3a,7a-?) -3-methoxy-1H-inden-1-yl)-dime thylmethanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3) ,3a,7a-?)-3-methoxy-1H-inden-1-yl)- Vo germanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1-(((1,1 ,2,3a,7a-?)-3-(((1,1- dimethylethyl)dimethylsilyl)oxy)-1H-inden-1-yl)dimethylsilyl)methanaminato(2-)-

N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-(((1,2,3,3a,7a-2)-3-(((1,1-dimeth Y. ylethyl)dimethylsilyl)oxy)-1H-inden-1-yl)methyl)silanaminato-(2-)-N-)dimeth yltitanium (N-(1,1-dimethylethyl)-2-((1,2,3, 3a,7a-7)-3-(((1,1- dimethylethyl)dimethylsilyl)oxy)-1H-inden-1-yl)-ethanaminato(2-)-

N)dimethyltitanium Yo (N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-2)-3-(((1,1- dimethylethyl)dimethylsilyl)oxy)-1H- inden-1-yl)-tetramethylethanaminato(2-)-

N)dimethyltitanium ty (N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-?)-3-(((1,1- dimethylethyl)dimethylsilyl)oxy)-1H- inden-1-yl)-1,2,2- tetramethyldisilanaminato(2)-N)dimethyltitanium (N-(1,1-dimethylethyl)-3-((1,2,3,3a,7a-?)-3 -((((1,1- dimethylethyl)dimethylsilyl)oxy)-1H-inden-1-yl)-propanaminato(2-)- °

N)dimethyltitanium (N-(1,1-dimethylethyl)-1-((1,2,3,3a,7a-?)-3-(((1,1- dimethylethyl)dimethylsilyl)oxy)-1H-inden -1-yl)-methanaminato(2-)-

N)dimethyltitanium (N-(1,1-dimethylethyl)-1-((1,2,3,3a,7a-2)-3-(((1,1- 1 dimethylethyl)dimethylsilyl)oxy)-1H- inden-1-yl)-dimethylmethanaminato(2-)-

N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(((1,1-dimethy lethyl)dimethylsilyl )oxy)-1H-inden-1-yl)-germanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1-(((1,2,3,3a,7a-?) -3-(1-piperidinyl)-1H-inden-1- Voyl)dimethylsilyl)methanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((( (1,2,3,3a,7a-?)-3-(1 -piperidinyl)-1H-inden- 1-yl)methyl)silanaminato-(2-)-N-)dimethyltitanium (N-(1,1 -dimethylethyl)-2-((1,2,3,3a,7a-?)-3-(1-piperidinyl)-1H-inden-1-yl)-ethanaminato(2-)-N)dimethyltitanium Y. ( N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-?)-3-(1-piperidinyl)- 1H-inden-1-yl)-tetramethylethanaminato(2-) -N)dimethyltitanium (N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-?)-3-(1-piperidinyl)-1H-inden-1-yl)-1 ,1,2,2- tetramethyldisilanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-3-((1,2,3,3a,7a-?)-3-(1-piperidinyl) )-1H-inden-1-yl)- Yo propanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1-((1,2,3,3a,7a-?)-3 -(1-piperidinyl)-1H-inden-1-yl)- methanaminato(2-)-N)dimethyltitanium z

(N-(1,1-dimethylethyl)-1-((1,2,3,3a,7a-?)-3-(1-piperidinyl)-1H-inden-1-yl)- dimethylmethanaminato(2-) -N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?)-3-(1-piperidinyl)-1H-inden- 1-yl)-germanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1-(((1,2,3,3a,7a-?)-3-(ethylmethylamino)-1H -inden-1-) ° dimethylsilyl)methanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-(((1,2,3,3a,7a- ? )-3-(ethylmethylamino)-1H-inden-1-yl)methyl)silanaminato-(2-)-N-)dimethyltitanium (N-(1,1-dimethylethyl)-2-((1,2,3) ,3a,7a-?)-3-(ethylmethylamino)-1H-inden-1-yl)-ethanaminato(2-)-N)dimethyltitanium 01

N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-?)-3-(ethylmethylamino)-1H-inden-1-yl)-tetramethylethanaminato(2-)-N) dimethyltitanium (N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-7)-3-(ethylmethylamino)-1H-inden-1-y1)- 1,1,2, 2-tetramethyldisilanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-3-((1,2,3,3a,7a-7)-3-(ethylmethylamino)-1H-inden-1 -yl)- \o propanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1-((1,2,3,3a,7a-?)-3-(ethylmethylamino)-1H -inden-1-yl)-methanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1-((1,2,3,3a,7a-7)-3-(ethylmethylamino) -1H-inden-1-yl)- dimethylmethanaminato(2-)-N)dimethyltitanium Y. (N-(1,1-dimethyl)-1,1-dimethyl-1-((1,2,3,3a, 7a-?)-3-(ethylmethylamino)-1H-inden-1-yl)-germanaminato(2-)-N)dimethyltitanium (N-cyclohexyl-1-(((1,2,3,3a,7a-? )-3-(1-pyrrolidinyl)-1H-inden-1-yl)dimethylsilyl)methanaminato(2-)-N)dimethyltitanium (N-cyclohexyl-1,1-dimethyl-1-(((1,2,3) ,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1- Yo yl)methyl)silanaminato-(2-)-N-)dimethyltitanium (N-cyclohexyl-2-((1,2) ,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)-ethanaminato(2- )-N)dimethyltitanium go (N-cyclohexyl-2-((1,2, 3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)-tetr amethylethanaminato(2-)-N)dimethyltitanium (N-cyclohexyl-2-((1,2,3) ,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)-1,1,2,2- tetramethyldisilanaminato(2-)-N)dimethyltitanium (N-cyclohexyl-3-( (1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)-prop ° anaminato(2-)-N)dimethyltitanium (N-cyclohexyl-1-( (1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden- 1-yl)-meth anaminato(2-)-N)dimethyltitanium (N-cyclohexyl-1-((( 1,2,3,3a,7a-2)-3-(1-pyrrolidinyl)-1H-inden-1-yl)-dime thylmethanaminato(2-)-N)dimethyltitanium \ (N-cyclohexyl-1,1- dimethyl-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)- germanaminato(2-)-N)dimethyltitanium (N-ethyl- 1-(((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)dimethyls ily)methanaminato(2-)-N)dimethyltitanium (N-ethyl -1,1-dimethyl-1-(((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1- \o yl)methyl)silanaminato-(2- )-N-)dimethyltitanium (N-ethyl-2-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)-ethanaminato(2-) -

N)dimethyltitanium (N-ethyl-2-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)-tetrameth ylethanaminato(2-)-N )dimethyltitanium Y. (N-ethyl-2-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)-1,1,2,2 -t etramethyldisilanaminato(2-)-N)dimethyltitanium (N-ethyl-3-((1,2,3,3a,7a-7)-3-(1-pyrrolidinyl)-1H-inden- 1-yl)- propanaminato(2-)-

N)dimethyltitanium (N-ethyl-1-((1,2,3,3a,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)-methanaminato(2-)- Yo

N)dimethyltitanium (N-ethyl-1-((1,2,3,3a,7a-?)-3~(1-pyrrolidinyl)-1H-inden-1-yl)-dimethylmethanaminato(2-)-N )dimethyltitanium

£1 (N-ethyl-1,1-dimethyl-1-((1,2,3,32,7a-?)-3-(1-pyrrolidinyl)-1H-inden-1-yl)- germanaminato(2 -)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1-(((;2,3,3a,7a-?)-2-methyl-3-(1-pyrrolidinyl)-1H-inden- 1- yl)dimethylsilyl)methanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-(((1,2,3,3a,7a-?)- 2-methyl-3-(1- ° pyrrolidinyl)-H-inden-1-yl)methyl)silanaminato-(2-)-N-)dimethyltitanium (N-(1,1-dimethylethyl)-2-((1 ,2,3,3a,7a-?)-2-methyl-3-(1-pyrrolidinyl)-1H-inden-1- yl)-ethanaminato(2-)-N)dimethyltitanium (N-(1,1- dimethylethyl)-2-((1,2,3,3a,7a-?)-2-methyl-3-(1-pyrrolidinyl)-1H-inden-1- yl)-tetramethylethanaminato(2-)-N)dimethyltitanium 001 (N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-?)-2-methyl-3-(1-pyrrolidinyl)-1H-inden-1- y)- 1,1,2,2-tetramethyldisilanaminato(2-)-N)dimethyltitanium(N-(1,1- dimethylethyl)-3 -((1,2,3,3a,7a-?)-2-methyl-3 -(1-pyrrolidinyl)-1H-inden-1-yl)-propanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1-((1,2,3,3a,7a- ?)-2-methyl-3-(1-pyrrolidinyl)-1H-inden-1- Voyl)-methanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1-((1 ,2,3,3a,7a-?))-2-methyl-3-(1-pyrrolidinyl)-1H-inden-1- yl)-dimethylmethanaminato(2-)-N)dimethyltitanium (N-(1,1 -dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-?))-2-methyl-3-(1-pyrrolidinyl)-1H-inden-1-yl)-germanaminato (2-)-N)dimethyltitanium Y- (1,1'-(2.sup.4-1,3-butadiene-1,4-diyl)bis(benzene))(N-(1,1-dimethylethyl) -1,1- dimethyl-1-((1,2,3,4,5-?)-3-(1-pyrrolidinyl)-2,4-cyclopentadien-1- yl)silanaminato(2-)-N) titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-2)-3-(1-pyrrolidinyl)-2,4-cyclopentadien-1 -yl)silanaminato(2-)-N)((1,2,3,4-?)-2,4-hexadiene)titanium Yo (N-(1,1-dimethylethyl)-1,1-dimethyl-1 -((1,2,3,4.5-1)-3-(1-pyrrolidinyl)-2,4- cyclopentadien-1-yl)silanaminato(2-)-N)((1,2,3,4- ?)-1,3-pentadiene)titanium ty ((2-(dimethylamino)methyl)phenyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1- ((1,,3,4, 5-7)-3-(1-pyrrolidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)titanium dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl- 1-((1,2,3,4,5-?)-3-(1-pyrrolidinyl)-2,4- cyclopentadien-1-yl)silanaminato(2-)-N)titanium (N-(1, 1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-?)-3-(1-pyrrolidinyl)-2,4- °cyclopentadien-1-yl)silanaminato(2 -)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-?)-3-(1-pyrrolidinyl)-2, 4- cyclopentadien-1-yl)silanaminato(2-)-N)bis(phenylmethyl)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4, 5-7)-3-(1-pyrrolidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)bis(phenylmethyl)bis((trimethyl 01 silyl)methyl)titanium (N-(1) ,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-?)-3-(1-pyrrolidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2 -)-N)bis(phenylmethyl)bis(2,2-dimeth ylpropyhtitanium (1,1-dimethyl-N-(phenylmethyl)-1-((1,2,3,4,5-?)-3-( 1-pyrrolidinyl)-2,4- \o cyclopentadien-1-yl)silanaminato(2-)-N)((1,2,3,4-?)-1,3-pentadiene)titanium ((2-( dimethylamino)methyl)phenyl)(1,1-dimethyl-N-(phenylmethyl)-1-((1,2,3,4,5- ?)-3-(1-pyrrolidinyl)-2,4cyclopentadien-1- yl)silanaminato(2-)-N)titanium dichloro(1,1-dimethyl-N-(phenylmethyl)-1-((1,2,3,4,5-?)-3-(1-pyrrolidinyl)- 2,4- cyclopentadien-1-yl)silanaminato(2-)-N)titanium Y. (1,1-dimethyl-N-(phenylmethyl)-1-((12,3,4,5-?)-3 -(1-pyrrolidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)dimethyltitanium (1,1-dimethyl-N-phenyl-1-((1,2,3,4,5) -2)-3-(1-pyrrolidinyl)-2,4-cyclopentadien-1- yl)silanaminato(2-)-N)dimethyltitanium (1,1-dimethyl-1-((1,2,3,4, 5?)-3-(1-pyrrolidinyl)-2,4-cyclopentadien-1-yl)-N- Yo ((tricyclo(3.3.1.1.3,7)dec-1-yl))silanaminato(2-) -N)dimethyltitanium (1,1-dimethyl-N-cyclododecyl-1-((1,2,3,4,5-?)-3-(1-pyrrolidinyl)-2,4-cyclopentadien-1-yl) silanaminato(2-)-N)dimethyltitanium

M (1,1-dimethyl-N-(phenylmethyl)-1-((1,2,3,4,5-?)-3-(1-pyrrolidinyl)-2,4- cyclopentadien- 1- yl)silanaminato(2-)-N)bis(phenylmethyl)titanium ‎.sup.4-1,3-butadiene- 1,4-diyl)bis(benzene))(1,1-dimethyl-N-(1 -methylethyl)- ?(-'1,1( 1-((1,2,3,4,5-7)-3-(1-pyrrolidinyl)-2,4-cyclopentadien-1-yl)silanaminato (2-)- Njtitanium ° (1,1-dimethyl-N-(1-methylethyl)-1-((1,2,3,4,5-7)-3-(1-pyrrolidinyl) -2,4- cyclopentadien-1-yl)silanaminato(2-)-N)((1,2,3,4-?)-2,4-hexadiene)titanium (1,1-dimethyl- N-(1-methylethyl)-1-((1,2,3,4,5-?)-3-(1-pyrrolidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-) -N)((1,2,3,4-?)-1,3-pentadiene)titanium ((2-(dimethylamino)methyl)phenyl)(1,1-dimethyl-N-(1-methylethyl) -1-((1,2,3,4,5- 01 ?7)-3-(1-pyrrolidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)titanium dichloro(1,1-dimethyl-N-(1-methylethyl)-1-((1,2,3,4,5-2)-3-(1-pyrrolidinyl)-2,4- cyclopentadien- 1-yl)silanaminato(2-)-N)titanium (1,1-dimethyl-N-(1-methylethyl)-1-((1,2,3,4,5-)-3-(1) -pyrrolidinyl)-2,4- cyclopentadien-1-yl)silanaminato(2-)-N)dimethyltitanium \o .sup.4-1,3-butadiene-1,4-diyl)bis(benzene) )(N-(1,1-dimethylethyl)-1,1- ?(<'1,1( dimethyl-1-((1,2,3,4,5-?)-3-(1- pyrrolidinyl)-2,4-cyclopentadien-1- yl)silanaminato(2-)N)titanium (N-ethyl-1,1-dimethyl-1-((1,2,3,4,5-) 7)-3-(1-pyrrolidinyl)-2,4-cyclopentadien-1- yl)silanaminato(2-)-N)((1,2,3,4-?)-2,4-hexadiene) titanium Y-.(N-ethyl-1,1-dimethyl-1-((1,2,3,4,5-7)-3-(1-pyrrolidinyl)-2,4-cyclopentadien-1- yl)silanaminato(2-)-N)((1,2,3,4-7)-1,3-pentadiene)titanium ((2-(dimethylamino)methyl)phenyl)(N-ethyl- 1-dimethyl-1-((1,2,3,4,5-?)-3-(1- pyrrolidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)titanium dichloro(N-ethyl-1,1-dimethyl-1-((1,2,3,4,5-?)-3-(1-pyrrolidinyl)-2,4- Yo cyclopentadien-1- yl)silanaminato(2-)-N)titanium (N-ethyl-1,1-dimethyl-1-((1,2,3,4,5-?)-3-(1-pyrrolidinyl)-2 ,4-cyclopentadien-1- yDsilanaminato(2-)-N)dimethyltitanium

£4 (1,1'(?.sup.4-1,3-butadiene-1,4-diyl)bis(benzene)(N-(1,1-dimethylethyl)-1,1-dimethyl-1- ( (1,2,3,4,5-7)-3-(1-piperidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)titanium (N-(1,1-dimethylethyl) )-1,1-dimethyl-1-((1,2,3,4,5-7)-3-(1-piperidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N )((1,2,3,4-?)-2,4-hexadiene)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4, 5-2)-3-(1-piperidinyl)-2,4-°cyclopentadien-1-yl)silanaminato(2-)-N)((1,2,3,4-7)-1,3-pentadiene )titanium ((2-(dimethylamino)methyl)phenyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-7)-3-( 1-piperidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)titanium -dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2) ,3,4,5-2)-3-(1-piperidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)titanium 001 (N-(1,1-dimethylethyl)-1 ,1-dimethyl-1-((1,2,3,4,5-7)-3-(1-piperidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)dimethyltitanium ( 1,1+?.sup.4-1,3-butadiene-1,4-diyl)bis(benzene))(N--(1,1-dimethylethyl)-1,1-dimethyl-1- ((1 ,2,3,4,5-7)-3(1-piperidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)titanium (N-(1,1-dimethylethyl)-1 ,1-dimethyl-1-((1,2,3,4,5-?)-3-(methylphenylamino)-2,4- \o cyclopentadien-1-yl)silanaminato(2-)-N)(( 1,2,3,4-7)-2,4-hexadiene)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-? )-3-(methylphenylamino)-2,4- cyclopentadien-1-yl)silanaminato(2-)-N)((1,2,3,4-?)-1,3-pentadiene)titanium ((2- (dimethylamino)methyl)phenyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-?)-3- (methylphenylamino)-2,4 -cyclopentadien-1-yl)silanaminato(2-)-N)titanium : Y. dichloro(N-(1,1-dimethylethyl)-1,1-methyl-1-((1,2,3,4,5) -?)-3-(methylphenylamino)- 2,4-cyclopentadien-1-yl)silanaminato(2-)-N)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-(( 1,2,3,4,5-? )-3-(methylphenylamino)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1, 2,3,4,5-2)-3-(methylphenylamino)- Ye 2,4cyclopentadien-1-yl)silanaminato(2-)-N)bis(phenylmethyl)titanium (N-(1,1-dimethylethyl)- 1,1-dimethyl-1-((1,2,3,4,5-?)-3-(methylphenylamino)-2,4- cyclopentadien-1-yl)silanaminato(2-)-N)bis(phenylmethyl) )bis((trimet hylsilyl)methyl)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-?)-3-(methylphenylamino)- 2,4- cyclopentadien-1-yl)silanaminato(2-)-N)bis(phenylmethyl)bis(2,2-dim ethylpropyl)titanium (1,1'«(? .sup.4-1,3-butadiene) -1,4-diyl)bis(benzene))(1-((1,2,3,4,5-7)-3- (dimethylamino)-2,4-cyclopentadien-1-yl)-N-( 1,1-dimethylethyl)-1,1-°imethylsilanaminato(2-)-N)titanium (1-((1,2,3,4,5-7)-3-(dimethylamino)-2,4-cyclopentadien -1-yl)-N-(1,1- dimethylethyl)-1,1-dimethylsilanaminato(2-)-N)((1,2,3,4-?)-2,4-hexadiene)titanium (1 -((1,2,3,4,5-7)-3-(dimethylamino)-2,4-cyclopentadien-1-yl)-N-(1,1- dimethylethyl)-1,1-dimethylsilanaminato(2) -)-N)((1,2,3,4-7)-1,3-pentadiene)titanium 01 ((2-(dimethylamino)methyl)phenyl)(1<((1,2,3,4, 5-?)-3-(dimethylamino)-2,4-cyclopentadien- 1-y1)-N<(1,1-dimethylethyl)-1,1-dimethylsilanaminato(2-)-N)titanium dichloro(1-( (1,2,3,4,5-7)-3-(dimethylamino)-2,4-cyclopentadien-1-yl)-N-(1,1- dimethylethyl)-1,1-dimethylsilanaminato(2-) -N)titanium (1-((1,2,3,4,5-7)-3-(dimethylamino)-2,4-cyclopentadien-1-yl)-N-(1,1- \o dimethylethyl) -1,1-dimethylsilanaminato(2-)-N)dimethyltitanium (1,1'-(?.sup.4-1,3-butadiene-1,4-diyl)bis(benzene))(N-(1, 1-dimethylethyl)-1- ((1,2,3,4,5-?7)-3-(ethylmethylamino)-2,4-cyclopentadien-1-yl)-1,1- dimethylsilanaminato(2-)- N)titanium (N-(1,1-dimethylethyl)-1-((1,2,3,4,5-?)-3-(ethylmethylamino)-2,4-cyclopentadien-1- Y.y1)- 1,1-dimethylsilanaminato(2-)-N)((1,2,3,4-?)-2,4-hexadiene)titanium (N-(1,1-dimethylethyl)-1-((1,2) ,3,4,5-?)-3-(ethylmethylamino)-2,4-cyclopentadien-1- yl)-1,1-dimethylsilanaminato(2-)-N)((1,2,3,4-2 )-1,3-pentadiene)titanium ((2-(dimethylamino)methyl)phenyl)(N«(1,1-dimethylethyl)-1-((1,2,3,4,5-?)-3- (ethylmethylamino)-2,4-cyclopentadien-1-y1)-1,1-dimethylsilanaminato(2-)-N)titanium Yo dichloro(N-(1,1-dimethylethyl)-1-((1,2,3) ,4,5-7)-3-(ethylmethylamino)-2,4-cyclopentadien-1-yl)-1,1-dimethylsilanaminato(2-)-N)titanium (N-(1,1-dimethylethyl)-1 -((1,2,3,4,5-7)-3-(ethylmethylamino)-2,4-cyclopentadien-1-

T11 yD)-1,1-dimethylsilanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1-((1,2,3,4,5-7)-3-(ethylmethylamino) )-2,4-cyclopentadien-1- yD-1,1-dimethylsilanaminato(2-)-N)bis(phenylmethyl)titanium (N-(1,1-dimethylethyl)-1-((1,2,3, 4,5-?)-3-(ethylmethylamino)-2,4-cyclopentadien-1- yD)-1,1-dimethylsilanaminato(2-)- °

N)bis(phenylmethyl)bis((trimethylsilyl)methyl)titanium (N~(1,1-dimethylethyl)-1-((1,2,3,4,5-?)-3-(ethylmethylamino)-2, 4-cyclopentadien-1-yl)-1,1- dimethylsilanaminato(2-)-N)bis(phenylmethyl)bis(2,2-dimethylpropyl)titanium (1,1'{(?.sup.4-1,3) -butadiene-1,4-diyl)bis(benzene))(N-(1,1-dimethylethyl)-1,1-dimethyl-1- ((1,2,3,4,5-2)-3- methoxy-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)titanium Ve (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4) ,5-?)-3-methoxy-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)((1,2,3,4-?)-2,4-hexadiene)titanium (N -(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-7)-3-methoxy-2,4-cyclopentadien-1-yl)silanaminato(2- )-N)((1,2,3,4-?)-1,3-pentadiene)titanium ((2-(dimethylamino)methyl)phenyl)(N-(1,1-dimethylethyl)-1,1- dimethyl-1-((1, \o 2,3,4,5-?7)-3-methoxy-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)titanium dichloro(N-( 1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-?)-3-methoxy-2,4-cyclopentadien-1-yl)silanaminato(2-)- N)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-?)-3-methoxy-2,4-cyclopentadien-1-yl )silanaminato(2-)-N)dimethyltitanium Y. (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-?)-3-methoxy- 2,4-cyclopentadien-1-yl)silanaminato(2-)-N)bis(phenylmethyl)titanium (1,1'-(? .sup.4-1,3-butadiene-1,4-diyl)bis(benzene))(N-(1,1-dimethylethyl)-1,1- dimethyl-1-((1,2,3,4) ,5-7)-3-((1,-dimethylethyl)oxy)-2,4-cyclopentadien-1- yl)silanaminato(2-)-N)titanium Yo (N-(1,1-dimethylethyl)-1 ,1-dimethyl-1-((1,2,3,4,5-?)-3-((1,1-dimethylethyl)oxy)- 2,4-cyclopentadien-1-yl)silanaminato(2-) -N)((1,2,3,4-?)-2,4-hexadiene)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3, 4,5-2)-3-((1,1-dimethylethyl)oxy)-

oY 2,4-cyclopentadien-1-yl)silanaminato(2-)-N)((1,2,3,4-?)-1,3-pentadiene)titanium ((2(dimethylamino)methyl)phenyl)( N~(1,1-dimethylethyl)-1,1-dimethyl-1((1,2,3,4,5-?)-3- ((1,1-dimethylethyl)oxy)-2,4-cyclopentadien -1-yl)silanaminato(2-)-N)titanium dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-?)-3 -((1,1- dimethylethyl)oxy)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)titanium ° (N-(1,1-dimethylethyl)-1,1-dimethyl-1 -((1,2,3,4,5-2)-3-((1,1-dimethylethylJoxy)- 2,4-cyclopentadien-1-yl)silanaminato(2-)-N)dimethyltitanium (N-( 1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-?)-3-(hexahydro-1H-azepin-1-yl)-2,4-cyclopentadien- 1-yl)silanaminato(2-)-N)dimethyltitanium - (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-7)-3- (hexahydro-1 (2H)-azocinyl)-01 2,4cyclopentadien-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((( 1,2,3,4,5-2)-3-(octahydro-1H-azonin-1-yl)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)dimethyltitanium (N-( 1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-2)-3-(octahydro-1(2H)-azecinyl)-2,4-cyclopentadien-1 -yl)silanaminato(2-)-N)dimethyltitanium \o (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-2)-3- (methyl(phenylme thyl)amino)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1 ,2,3,4,5-2)-3-((1,1-dimethylet hyl)methylamino)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1) ,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-2)-3-(methyl1,1-methyY.lethyl)amino)-2,4-cyclopentadien- 1-yl)silanaminato(2-)-N)dimethyltitanium (N~(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-2)-3-( methylphenylamino)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4) ,5-?)-3-(dimethylphosphino)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)dimethyltitanium Yo (N-(1,1-dimethylethyl)-1,1-dimethyl-1 -((1,2,3,4,5-y1)-3-(diphenylphosphino)-2,4- cyclopentadien-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl) )-1,1-dimethyl-1-((1,2,3,4,5-?)-3-(methylphenylphosphino)- ya.

oy 2,4cyclopentadien-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-2) )-3-ethoxy-2,4-cyclopentadien- 1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2, 3,4,5-?)-3-propoxy-2,4-cyclopentadien- 1-yl)silanaminato(2-)-N)dimethyltitanium ° (N-(1,1-dimethylethyl)-1,1-dimethyl- 1-((1,2,3,4,5-?))-3-(1-methylethoxy)-2,4- cyclopentadien-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1) ,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-2)-3-(phenoxy)-2,4-cy clopentadien-1-yl)silanaminato(2- )-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-2))-3-(phenylthio)-2,4- 01 cyclopentadien-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-?)- 3-(methylthio)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)dimethyltitanium (1,1'-(2.sup.4-1,3-butadiene-1,4-diyl) bis(benzene))(N-(1,1-dimethylethyl)-1,1- dimethyl-1-((1,2,3,4,5-?)-2-methyl-3-(1-pyrrolidinyl) -2,4-cyclopentadien-1-yl)sil \o anaminato(2-)-N)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3, 4,5-?)-2-methyl-3-(1-pyrrolidinyl)- 2,4-cyclopentadien-1-yl)silanaminato(2-)-N)((1,2,3,4-?)- 2,4-hexadiene)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-7)-2-methyl-3-(1- pyrrolidinyl)- 2 4-cyclopentadien-1-yl)silanaminato(2-)-N)((1,2,3,4-7)-1,3-pentadiene)titanium \ ((2-(dimethylamino)methyl) phenyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-7)-2-methyl-3-(1-pyrrolidinyl)-2, 4cyclopentadien-1-yl)silanaminato(2-)-N)titanium dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-2)- 2-methyl-3-(1-pyrrolidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1- ((1,2,3,4,5-?)-2-methyl-3-(1-pyrrolidinyl)- Yo 2,4-cyclopentadien-1-yl)silanaminato(2-)-N)dimethyltitanium (1, 1'-(? .sup.4-1,3-butadiene-1,4-diyl)bis(benzene))(N-(1,1-dimethylethyl)-1,1- dimethyl-1-((1,2,3,4) ,5-?)-2-propyl-3-(1-pyrrolidinyl)-2,4-cyclopentadien-1-yl)sil of anaminato(2-)-N)titanium (N-(1,1-dimethylethyl)- 1,1-dimethyl-1-((1,2,3,4,5-?)-2-propyl-3-(1-pyrrolidinyl)- 2,4-cyclopentadien-1-yl)silanaminato(2-) -N)((1,2,3,4-?)-2,4-hexadiene)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3, 4,5-?)-2-propyl-3-(1-pyrrolidinyl)- 2,4-cyclopentadien-1-?)silanaminato(2-)-N)((1,2,3,4-?)- 1,3-pentadiene)titanium ° ((2-(dimethylamino)methyl)phenyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1, 2,3,4,5- 7)-2-propyl-3-(1-pyrrolidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N) titanium dichloro(N-(1,1-dimethylethyl)-1,1- dimethyl-1-((1,2,3,4,5-?)-2-propyl-3-(1- pyrrolidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)titanium 01 (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-2)-2-propyl-3-(1-pyrrolidinyl)- 2,4 -cyclopentadien-1-yl)silanaminato(2-)-N)dimethyltitanium (1,1'-(?.sup.4-1,3-butadiene-1,4-diyl)bis(benzene))(N-( 1,1-dimethylethyl)-1,1- dimethyl-1-((1,2,3,4,5-?)-2-methyl-4-ethyl-3-(1-pyrrolidinyl)-2,4- cyclopentadien- 1- yl)silanaminato(2-)-N)titanium \o (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-?) -2-methyl-4-ethyl-3-(1- pyrrolidinyl)-2,4cyclopentadien-1-yl)silanaminato(2-)-N)((1,2,3,4-)-2,4- hexadiene )titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-2)-2-methyl-4-ethyl-3-(1- pyrrolidinyl) )-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)((1,2,3,4-?)-1,3- Y.pentadiene)titanium ((2-(dimethylamino)methyl )phenyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1- ((1,2,3,4,5-?)-2-methyl-4-ethyl-3-(1- pyrrolidinyl)-2,4-cyclopentadien-1- yl)silanaminato(2-)-N)titanium dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3, 4,5-2)-2-methyl-4-ethyl-3-(1-00 pyrrolidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)titanium (N-(1,1) -dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-?)-2-methyl-4-ethyl-3-(1-pyrrolidinyl)-2,4-cyclopentadien-1 -yl)silanaminato(2-)-N)dimethyltitanium oo (1,1'-(?.sup.4-1,3-butadiene-1,4-diyl)bis(benzene))(N-(1,1 -dimethylethyl)-1,1- dimethyl-1-((1,2,3,4,5-?)-3-(1-methylethyl)-4-(1-pyrrolidinyl)-2,4-cyclopentadiene- 1 -yl)silanaminato(2-)-N)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-7)-3-(1 -methylethyl)4-(1-pyrrolidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)((t,2,3,4-2)-2,4-°hexadiene)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-?)-3-(1-methylethyl)4-(1- pyrrolidinyl)-2 ,4-cyclopentadien-1-yl)silanaminato(2-)-N)((1,2,3,4-?)-1,3- pentadiene)titanium ((2-(dimethylamino)methyl)phenyl)(N -(1,1-dimethylethyl)-1,1-dimethyl-1-1 ((1,2,3,4,5-2)-3-(1-methylethyl)-4-(1-pyrrolidinyl)-2 ,4-cyclopentadien-1- yl)silanaminato(2-)-N)titanium dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-) 2)-3-(1-methylethyl)4-(1- pyrrolidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)titanium (N-(1,1-dimethylethyl)-1, 1-dimethyl-1-((1,2,3,4,5-2)-3-(1-methylethyl)-4-(1- \o pyrrolidinyl)-2,4-cyclopentadien-1-yl)silanaminato (2-)-N)dimethyltitanium (1,1'-(?.sup.4-1,3-butadiene- 1,4-diyl)bis(benzene))(N-(1,1-dimethylethyl)-1 ,1- dimethyl-1-((1,2,3,4,5-?)-2,4,5-trimethyl-(1-pyrrolidinyl)-2,4-cyclopentadien-1-y

D)silanaminato(2-)-N)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-2)-2,4,5 -trimethyl-(1- Y.pyrrolidinyl)-2,4cyclopentadien-1-yl)silanaminato(2-)-N)((1,2,3,4-2)-2,4-hexadiene)titanium (N- (1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-?)-2,4,5-trimethyl-(1- pyrrolidinyl)-2,4-cyclopentadien -1-yl)silanaminato(2-)-N)((1,2,3,4-7)-1,3- pentadiene)titanium Yo ((2-(dimethylamino)methyl)phenyl)(N-(1 ,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-7)-2,4,5-trimethyl-(1-pyrrolidinyl)-2,4-cyclopentadien-1 -yl)silanaminato(2-) -N)titanium dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,4,5-7)-2,4 ,5-trimethyl-(1-pyrrolidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-( (1,2,3,4,5-2)-2,4,5-trimethyl-(1- pyrrolidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)dimethyltitanium (N- (1,1-dimethylethyl)-1-methyl-1-phenyl-1-((1,2,3,4,5-?)-3-(1-pyrrolidinyl)-2,4-°cyclopentadien-1- yl)silanaminato(2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-diphenyl-1-((1,2,3,4,5-?)-3-(1-pyrrolidinyl)-2,4-cyclopentadien-1- yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-bis(1-methylethoxy)-1-((1,2,3,4,5-?1) -3-(1-pyrrolidinyl)-2 4-cyclopentadien-1-yl)silanaminato(2-)-N)dimethyltitanium 01 (N-(1,1-dimethylethyl)-1-ethoxy-1-methyl-1-( (1,2,3,4,5-2)-3-(1-pyrrolidinyl)-2,4- cyclopentadien-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl) )-1,1-dimethoxy-1-((1,2,3,4,5-2)-3-(1-pyrrolidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N )dimethyltitanium (N-(1,1-dimethylethyl)-2-((1,2,3,4,5-?)-3-(1-pyrrolidinyl)-2,4-cyclopentadien-1- Voyl)ethanaminato (2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-2-((1,2,3,4,5-?)-3-(1-pyrrolidinyl)-2,4-cyclopentadien- 1-yl)- 1,1,2,2-tetramethylethanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-2-((1,2,3,4,5-?)- 3-(1-pyrrolidinyl)-2,4-cyclopentadien-1-yl)- 1,1,2,2-tetramethyldisilanaminato(2-)-N)dimethyltitanium XY. (N-(1,1-dimethylethyl)-3-((1,2,3,4,5-?)-3-(1-pyrrolidinyl)-2,4-cyclopentadien-1-yl)-propanaminato(2 -)-N)dimethyltitanium (N-(1,1-dimethylethyl)-2-((1,2,3,4,5-?)-3-(1-pyrrolidinyl)-2,4-cyclopentadien-1-

yDmethylaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-2-((1,2,3,4,5-?)-3-(1-pyrrolidinyl)-2,4-cyclopentadien -1-yl)- Yo 1,1-dimethylmethanaminato(2-)-N)dimethyltitanium : (N-(1,1-dimethylethyl)-2-((1,2,3,4,5-7)-3 -(1-pyrrolidinyl)-2,4-cyclopentadien-1-yl)- 1,1-dimethylgermanaminato(2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-2)4,5,6,7-tetrahydro-3-(1-) pyrrolidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2) ,3,3a,7a-?)4,5,6,7-tetrahydro-3- (methyl(1-methylethyl)amino)-2,4-cyclopentadien-1-yl)silanaminato(2-)- N)dimethyltitanium ° (N-(1,1-dimethylethyl)-1,1-dimethyl-1(1,2,3,3a,7a-?)4,5,6,7-tetrahydro-2- methyl-3-(1-pyrrolidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)dimethyltitanium (N-(1,1-dimethylethyl)-1,1-dimethyl- 1-((1,2,3,3a,7a-?)-4,5,6, 7-tetrahydro-2,4,5- trimethyl-3-(1-pyrrolidinyl)-2,4-cyclopentadien -1-ylsilanaminato(2-)- N)dimethyltitanium 01 (N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-?)-4,5,6 ,7-tetrahydro-3-(1-pyrrolidinyl)- 2,4-cyclopentadien-1-yl)silanaminato(2-)-N)dimethyltitanium (N-methyl-1,1-dimethyl-1-( (1,2,3,3a,7a-?)-4,5,6,7-tetrahydro-3-(1-pyrrolidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-)- N)dimethyltitanium dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-2)4,5,6, 7-tetrahydro-3 - \o ‎(1-pyrrolidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)titanium (N-(1,1-dimethylethyl)-1,1-dimethyl-1 -((1,2,3,3a,7a-?)4,5,6,7-tetrahydro-3-(1- pyrrolidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-) -N)((1,2,3,4-?)-1,3- pentadiene)titanium ((2-(dimethylamino)methyl)phenyl)(N-(1,1-dimethylethyl)-1 ,1-dimethyl-1- Y. ((1,2,3,3a,7a-?)-4,5,6,7-tetrahydro-3-(1-pyrrolidinyl)-2,4-cyclopentadien- 1- yD)silanaminato(2-)-N)titanium (N-(1,1-dimethylethyl)-1,1-dimethoxy-1-((1,2,3,3a,7a-?) 4,5,6,7-tetrahydro-3-(1- pyrrolidinyl)-2,4-cyclopentadien-1-yl)silanaminato(2-)-N)dimethyltitanium (1-((1,2, 3,3a,6a-?)-3-(dimethylamino)-1,4,5,6-tetrahydro- 1-pentalenyl)-N-(1,1- Yo dimethylethyl))-1,1-dimethylsilanaminato( 2-)-N)dimethyltitanium (1-((1,2,3,3a,6a-2)-3-(dimethylamino)-1,4,5,6-tetrahydro-1-pentalenyl)-N- (1,1- dimethylethyl))-1,1-dimethylsilanaminato(2-)-N)((1,2,3,4-?)-1,3-pentadiene)titanium oA ((2-( dimethylamino)methyl)phenyl)(1-((1,2,3,3a,6a-?)-3-(dimethylamino)-1,4,5,6- tetrahydro-1-pentalenyl)-(N-1, 1-dimethylethy))-1,1-dimethylsilanaminato(2-)-N)titanium (1-((1,2,3,3a,6a-?)-3-(dimethylamino)-1,4,5,6 -tetrahydro-1-pentalenyl)-N-(1,1- dimethylethyl))-1,1 -dimethoxysilanaminato(2-)-N)dimethyltitanium (1-((1,2,3,3a,6a-7)- 3-(diethylamino)-1 »4,5,6-tetrahydro-1-pentalenyl)-N-(1,1- ° dimethylethyl))-1,1-dimethylsilanaminato(2-)-N)dimethyltitanium (N-cyclohexyl) -(1-((1,2,3,3a,6a-?)-3 -(dimethylamino)-1,4,5,6-tetrahydro-1- pentalenyl))-1,1 -dimethylsilanaminato(2-) -N)dimethyltitanium (1-((1,2,3,3a,6a-?)-3-(dimethylamino)-2methyl 1 ,4,5,6-tetrahydro-1-pentalenyl)-N- (1,1 -dimethylethyl))-1,1 -dimethylsilanaminato(2-)-N)dimethyltitanium 1 (1-((1,2,3,3a,6a-?)-3-(dimethylamino)-4-methyl-1,4 ,5 ,6-tetrahydro-1-pentalenyl)-N- (1,1-dimethylethyl))-1,1 -dimethylsilanaminato(2-)-N)dimethyltitanium (1-((1,2,3,3a,6a) -?)-3~(dimethylamino)-4,5,6-trimethyl-1,4,5,6-tetrahydro-1- pentalenyl)-N-(1,1-dimethylethyl))-1,1 -dimethylsilanaminato( 2-)-

N)dimethyltitanium \o (1-((1,2,3,3a,6a-7)4-ethyl-3 -(dimethylamino)-1,4,5,6tetrahydro-1-pentalenyl)-N- (1, 1-dimethyl ethyl))-1,1 -dimethylsilanaminato(2-)-N)dimethyltitanium The complexes can be prepared using well-known synthetic methods. Experimentally, a reducing agent can be used to produce complexes of the less oxidation state. This process is described by hay 0 in US Patent Application Sequential No. 711077/4 Filed at VY May +10 64 Publication No. 15/100017 WO and information about which is included herein by way of Ref. The reactions are carried out in a suitable non-interfering solvent at a temperature ranging from -001 to 1007°C, preferably from 100°C; The most preferred is from zero to 90 m. And by the term "reducing agent" here he means a metal or a compound that causes; under conditions of vo reduction; metal reduction 24; from the higher oxidation state to the lower oxidation state. Examples of suitable metal reducing agents include base metals or ground base metals, aluminum and zine; Alkali metals or metalloids

04 Ground base Sodium Jie [sodium mg (38) and a sodium ingot [sodium potassium]. Examples of suitable reducing compounds are sodium naphthalenide, potassium graphite, and the structure is lithium. lithium alkyls » lithium alkadienyls or potassium and Griganrd M reagents Preferably reducing agents are base metals or ground base metals ¢ and in particular metal lithium Iithium or magnesium . Reaction media suitable for the formation of complex compounds include aliphatic hydrocarbons and aromatics; cyclic ethers; and, in the form of ala, branched-chain hydrocarbons, Jie, isobutane, butane, pentane 0. hexane, heptane, ocatne and mixtures thereof; clicyclic hydrocarbons and aliphatic for example cyclohexane ¢ cycloheptane; methyleyclohexane a methyleyclohexane; methylcloheptne ¢ and mixtures thereof; aromatic compounds and aromatic compounds substituted with hydrocarbyl Ve, such as benzyl, toluene, xylene, and dialkyl ethers B©-,©; dialkyl ether derivatives ©-:© of (poly)alkylene glycols ; Fourth, tetrahydrofuran. And mixtures of previous compounds are also. It shows a single method of preparation of substituent cyclopentadienyl groups © - offending seed ; which are useful as starting materials for constrained geometry (CGC) catalyst systems or assemblies in Scheme 1 below; where: (a) reflux of an excess amount of amine “benzene” for 74 hours (-H;0); (lb) excess amount of amine (A) eq.); 12704 1 (equivalent) in Cl 0112; sagram; Add the ketone and number by heating to Yo m ¢ (@ 05 eq of Buli -0/hexane at Yo Yo m c (3) - 1.0 eq Cl - silane THF [ silane at Yo m ; (e) 001 McAfee of tan3-0/hexane at Yo m .

Ne 11 selected separately in each case is RM (RYT +R Lee directly attached to the cyclopentadienyl ring nitrogen except on the tyrogen Lad) caryl, aryl A cycloalkyl or alkyl cycloalkyl any alkyl (cyclopentadienyl ring) and is not limited to these groups only. in rR "J .

H ab: deaf 1 yo - yen

H RY, b \- RR > i er

R 1 sa is a region called from Vo in position nitrogen being the substituent containing an offending atom with nitrogen is a different substituent for conversion to 1-Indanone indanone -1 and the indenyl system is The analogues of adenyl, although the composition of the latter is not limited to the use of enamine, indanone, enamines this compound. Preferably, enamines are formed by methods known in the art involving condensation of secondary amines with a ketone, and the enamines may be removed (Noland, V. Kameswaran J. Org. Chem. 1981, 46, 1940-1 944) using a solvent. of benzene or toluene azeotropically corresponding aqueous secondary A

under reflux conditions and optionally an acid catalyst 8010 such as p-toluene sulfonic acid and with ketones with the largest stereoisomeric disability ¢ Nie "- 2-methyl-1-indanone ¢ or more volatile amines e.g. dimethylamine; it may be preferable to use stronger dehydration agents e.g. titanium chloroamides All) produced on site from titanium tetrachloride and an amine Condensation) 0 38, 1948 , 49-53 (Nilsson Acta Chemica Scandiavica B) These two methods have been used to produce substituted enamines in the oY ¥ positions of the indene. (Preferably the Y = position is linked to silicon Or other bonding moiety in the following compounds).

Erdik; M, Ay Chem.

Rev., 1989, 89, 1947-1980) + For the following formation of highly pure CGC ligands; The inamines prepared by these methods must be very pure and free from 1 by-products consisting of a ketone detone; Adol 81001 and the higher molecular weight reaction that typically accompany product formation. Uf of the aforementioned methods does not regularly give a product that can be used without any other type of technology. We have found that the chromatography technique using silica gel or alumina. The flash type rapidly prepares the hydrolysis of enamide to amine morokitone; As an unwanted result ©. Although these compounds are highly sensitive to water and air, enamines of this nature may be purified by careful fractional distillation or purification. recrystallization. In particular; A rapid distillation of anandanone enamines is required to prevent thermal polymerization in the distillate at a high temperature. Pure amine can be costly converted to its corresponding anionic salt to yield a very pure 000 vo ligand; Since enamines may also be sensitive to photochemical reactions 0 ny substituted CGC endanone is also a preferred starting material for ligands -1 is considered for oxygen at the *- position, and in particular  the enol ethers can be synthesized at this position By dehydration of the appropriate hemictal formed in situ from the andanone and the alcohol

L.A. Paquctte; A. Varararajan; E.Bey j. Am. Chem. Soc. In the presence of warm or acidic indanones, the indanones form ethers. (1984, 106, 6702-6708 ©) and are very sensitive Ald; also subject to degradation enamine, which are similar to enamine analogues, and when purified, they are converted more cost-effectively into oxygen: The corresponding, shown in Scheme 7, follows in which the anionic salts / n-Buli eq. and / 0-3: Ti is equivalent to an alkyl (oxygen) (except for those on oxygen H, a case-by-case form; nor is aralkyl “alkaryl” aryl “aryl” cycloalkyl » alkyl are limited only to these groups. 1 chart \o

XS

R or' ® deken eo] ether ° enol aber anion

Li® i i

RA

AN8.

R™ Nr wr A

H > i oH av Article 217 in blog

Lt Dr 750 coc tigmd COC diznicn

1y and when purified to a large extent; The conversion of amine to its corresponding anionic salt may be accompanied by reaction with an appropriate base of suitable concentration in a non-interfering solvent under anaerobic conditions. non-hydrophilic; The anionic-solid salt may often be filtered, washed and dried to yield an almost quantitative yield. likewise; The ethers of the ahenol (hydrogen) to the anionic salt proton indanone can remove the proton -1M. Approved landscapes (CGC) with a restrictive geometry (ligands) and the formation of ligands 71 p. 1 depends on indies substituted with a different atom on the anionic alkylation method shown by with cyclopentadienyl electrophiles where the cyclopentadienyl anion reacts Such as alkyl electrophiles (carrying the negative charge or acceptors of electrons 0 cyclo-Judy electrophiles to give penta-silylamines or halogenated secondary silyamines corresponding or cyclopentadienyl cyclopentadienyl alkylamines). Under the halogenated secondary cyclopentadienyl silylamines alkyl imines include, for example, (tertiary butyl) silyl or halogenated silyl or (tert-butyl) (chlorodimethylsilyamine, chloro dimethylsilyl)amine vo or (t-butyl)(chlorodimethylsilylmethyl)amine (chlorodimethylsilylmethyl)amine ¢ (t-butyl)(bromomethyldimethylsilyl)amine (tert-butyl)amine (bromomethylsilyl)amine (chlorodimethylsilyl)amine (phenyl)amine (chlorodimethylsilyl) ¢ (adamantyl)(chlorodiphenylsilylyamine disilyl)amine 0 (benzyl) (chlorodimethylsilyl)amine (chlorodimethylsilyl)(cyclohexyl)amine (cyclohexyl)amine (terti-butyl) (chloromethyl (benzyl)(chlorodimethylsilyl)amine methylsilyl)amine eg; » (t-butyl)(chloromethylphenylsilyl)amine phenylsilyl)amine to a molecular excess of ( Butyl THF gives the addition of a lithium derivative of the salt a drop in

THF in (t-butyl)(chlorodimethylsilyl)amine (tri) (chlorodimethylsilyl)amine vo electrophile and an excess of lithium chloride followed by a standard mol of lithium chloride may be used thereafter without further purification . It may be high ola aad often AR

Can the so-called ligand COC be converted into its insoluble di-iones by the reaction of the free base with ? Equivalent of a base of appropriate concentration in a non-interfering mol solvent. and by suitable non-interfering solvent in the half of the present invention means a solvent that does not interfere with the formation of; or interacts maliciously with; desired output. Such solvents suitable for the preparation of ionic salts and A salts include the ions of the subject of the invention; But without limitation on aliphatic and aromatic hydrocarbons, especially straight and branched-chain hydrocarbons such as butane, pentane, hexane, heptane 0, octane Decane » including its branching isomers and mixtures of Leia ; alicyclic hydrocarbons and alicyclic aliphatics such as cyclohexane ¢ cycloheptane » methyleyclohexane » methylcycloheptane » and mixtures thereof ¢ aromatic compounds substituted with hydrocarbyl such as benzene benzene vo, toluene, rylene, xylene, ethylbenzene, diethylbenzene, mixtures of terminators and cyclic ethers; In particular dialkyl ethers, B©-0, Sia, dibutyl ether, methyl-t-butyl ether, diakyl ether, Cp-Cg dialkyl ether, and derivatives (multi) alkylene glycols (poly)alkylene glycols ; Jia Thani Michox Od Uy » dimethoxyethane 0 THF dioxane and mixtures thereof. Mixtures of the above are also suitable. Jad, Bases of appropriate titres for the preparation of dianionic salts, the subject of the invention, on hydrocarbyl salts from de gonad metals 1; group oF and in particular alkyl or aryl salts aryl of yo lithium a lithium ¢ magnesium » as methyllithium, ethyllithium ethyllithium, s-butyllithium, n-butyllithium secondary, n-butyllithium, tert-butyllithium t -butyllithium and phenyl to phenyllithium

M “, Ji fe methyl magnesium chloride, ethyl magnesium bromide, pit le i-propyl magnesium chloride, dibutylmagnesium, (butyl) (Jy) dibutylmagnesium, (butyl)(ethyl)magnesium, dihexylmagnesium 0 ; And the metals of group 1 or group 7 are: lithium, sodium, potassium, magnesium, hydrates of group 1, group Y, or group 1 of the metals. ; Such as lithium hydride, sodium hydride, potassium hydride, or lithium aluminum hydride; complex 0 metal amide metalamine compounds group 1 or group 1 ; Jie is lithium diisopropylamide, lithium diisopropylamide, lithium dimethylamide, lithium hexamethyldisilazane, sodium hexamethyldisilazane, sodamide, and magnesium diisopropylamide. The anionic salts 1 subject of the invention on the foregoing, in addition to complex compounds of alkoxide metals of group 1 or group oF, such as sodium ethoxide, trisodium butyroxide, potassium butoxide, and potassium amylate 0. There is another preparatory attempt to form a ligand with a free base that includes on the reaction of an anionic salt of indenyl with an excess amount of bis-electrophylls; For example 0 : dichloromethylsilane in a polar solvent ¢ is "neutral" aprotic as le, . THF in an unexpected way + It was found that this attempt, in relation to the aforementioned purification of many groups of ligands replaced by a different atom in the position? in a; A significant portion of the ligand (byproduct of the diaclkyl additive) is often formed in spite of the use of an excessive amount of electrophile; As shown in Diagram 7 in the following vo |: Ya.

y 1 1 0. kr 6 qm + Ry 10eq ' y NR'y RY : 2 RN . Ansa-Ligaod ‏=” RY : : | J: : Z Na Cf Name The ease of preparation for this attempt depends on the stereoscopic and electronic considerations °. The conversion to a metal of the two-anion salt may be done by methods mentioned in the field as well. The interaction of the diionic salt in 7117 with Tic; (THF); followed by oxidation by methylene chloride or lead dichloride method and then studied (J.

Okuda, 8. lua Verch, 1. P.

Spaniol, R.

Storm Chem.

Ber., 1996, 129, 1429-1431, 13. Devore Ep 514,828. 01 which gives a complex of titanium (IV) dichloride . The dichloride may be silylated or hydrocarylated by denaturing the ligand with an appropriate silyl or hydrocarbyl converting agent; Such as Methyl Lithium, Methyl Magnesium Benzyl Potassium Chloride, Allyl Lithium, Trimethylsilyl Methyl Lithium, Neopentylmagnesium Bromide and Lithium Phenyl dug. A complete list of suitable silyl or hydrocarbyl curing agents is given below.

That is, a general method for producing dina from titanium diene (I) from the corresponding titanium (IV) dichloride has been shown by Devore and coworkers (D.

D.

Devore, FJ.

Timmers, D.L.Hasha, R.

K.

Rosen, T.

J.

Marks, P.

A. Deck, C.

L.

Stem, Organometallics. 1995, 14, 3132-3134; D.D.

Devore F.

J. M Timmers, J.

C.

Stevens, R. 1. Mussell, L.H Crawford, D.

R.

Wilson U.S.

Pat.

No. 5,556, 982. (AYA 00) (0) Hence ¢ treatment of dichloride with lithium tert-butyl in the presence of a masked diene yields the corresponding titanium diene (ID) complex for atom-substituted systems The complex (IT) metal compounds (CGC) can be formed according to the invention by any of the several methods of preparation, among which we find the following: The reaction is carried out under anaerobic and anaerobic conditions for the di-anionic salts of the metals valence ADEN; Jia metal halide or alkoxide complexes (ID) of the group; optionally followed by conversion to silyl A hydrocarbyl by suitable silyl or hydrocarbyl conversion agents to form VO complex halide, alkoxide, or The corresponding CGC(IV) silyl or hydrocarbyl(ID) is the subject of the invention.Another method of preparation comprises reduction of a complex of a suitable CGC (IV) dihalide or dioxide metal;or conversion to a monosilyl or monohydrocarbyl thereof;the complex of The corresponding mono-halide, alkoxide, silyl (Ye) or hydrocarbyl (CGC (AV) JB) analog by a reducing agent to a complex compound of the corresponding halide, alkoxide, silyl or hydrocarbyl metal (CGC am). It has been found to be particularly suitable for the preparation of complex CGC (I) metal compounds according to the invention by the methods shown by Wilson (D.

R.

Wilson’). US Patent No. 774 204 00 1997) which is provided herein by reference ve. For example cyclopentadienyl ligands can be substituted for

M1 with di-anionic salts or by (AB) agents for the conversion to hydrocarbyls of metal complexe of group 1 containing cyclopentadienyl in +3 oxidation to give CGC (I) complex metal compounds The subject of the invention.

° Reducing agents suitable for the reduction of the oxidation state of complex metal compounds of the metal CGC (IV) from £4 to +© have been shown previously and include, in particular, zinc, aluminum and magnesium.

Conversion agents include silylating and hydrocarbylating

suitable for CGC (I) and CGC (IV) propyl, ethyl and methyl complexes; Such as the methyl alkyl subject of the invention on the alkyl 0 phenyl teryl Jia ¢ aryl; aryl hexyl neopentyl neopentyl butyl

naphthyl, bisphenyl ¢ and aralkyl; Like benzyl and toluyl

methyl tolylmethyl and diphenylmethyl diphenyl methyl ; and alkaryl; like tulle

tolyl and xylyl; Allyl substituted with a silyl or an alkyl Jie ¢ alkyl methyl allyl

dimethylallyl, trimethylsilyl allyl 1, and dimethylallyl 0

trimethylallyl; Trialkylsilyl + as trimethylsilyl

1 and a third of triethylsilyl Jil; and tertiary alkyl silyl alkyl

Jie » trialkylsilylalkyl trimethylsilylmethyl ; pentadienyl

Jina; such as silyl or alkyl pentadienyl substituted silyl; pentadienyl

0 methylpentadienyl, dimethylpentadienyl and trimethyl

trimethylsilylpentadienyl and repeated (trimethylsilyl)pentadienyl

bis(trimethylsilyl)pentadienyl cyclohexadienyl and dimethylhexa

dimethylcyclohexadienyl ¢ dialkylaminoalkaryl dialkylaminoalkaryl ¢

as 0~(N,N-dimethylaminomethyl)phenyl; and di-alkyl amino aralkysyl

dialkylaminoaralkyl Ye » eg ORFO = (10 » 28 dimethyl (sind benzyl)

1 or 1;1 group metals; vinyl; 0-(N,N-dimethylamino)benzyl metal salts.! pal ¢ potassium Sodium lithium, preferably lithium salts

magnesium and aluminum Detailed silylating or hydrocarbylating agents include trimethylaluminum, methyllithium, methyl magnesium chloride, neopentyllithium chloride trimethylsilylmethyl magnesium chloride© and phenyllithium. Also included are hydrocarbyl conversion agents containing a (Towon) stabilizing group; In particular the hydrocarbyl conversion agents containing taone groups and the arms of the hydrocarbyl groups containing the taone group described in US Patent Application No. (YY E 04 0 whose salts include, for example, benzyl 0 K = N ¢ N) -7 ¢ benzyl potassium dimethylamino)benzylithium -2-07,11 dimethylamino)benzyllithium » allylithium and dimethylpentadienyl potassium. serial 8007; filed on January 71, 1497 (which corresponds to the international patent €0 (7/18) of which Lead 0 is given here by reference. The favored halides or alkoxides of compounds complexed with halides include halide or metal (IM) alkoxide complexes and halide complexes of CGC (III) alkoxide complexes ill contain fluoride, chloride, bromide, and methoxide ionide (—uS gira g iodide, ethoxide 1S $i) Ye, isopropoxide, i-propoxide, n-propoxide, butoxide, and phenoxide. alkoxide complexes that are preferred over titanium (II) chloride, titanium (II) ethoxide, titanium (II) bromide, and titanium isopropoxide (ID titanium) and (isopropoxide) (dichloro) 0 titanium (IMD) (dichloro)(isopropoxide), in addition to complex compounds of the Lewis base of the aforementioned complex compounds, especially those made of esher; In particular, the complex compounds of diethyl ether, tetrahydrofurate and glycol ether, ton A,

Vv. My favorite from the group; metal complexes, including. The complex metal compounds +3 + present in the cyclopentadienyl oxidation state containing triscyclopentadienyl titanium chloride include triscyclopentadienyl titanium oxidation and biscyclopentadienyl titanium chloride biscyclopentadienyl titanium chloride and bis biscyclopentadienyl titanium isopropoxide 0 biscyclopentadienyl titanium bromide cyclopentadienyl titanium dichloride cyclopentadienyl titanium ium diphenoxide or refined chloride ( Trimethylsilyl) tricyclopentadienyl titanium dimethoxide bis((trimethylsilyl)(t-butyl)cyclopentadienyl) zirconium 0 is the subject of this ligands and the ligands are — butyl)eyclopentadienyl)zirconium chloride substituted in pentadienyl containing PENTADINYL ligands The invention consists of ligands: a dissimilar seed where the ligand is in the form of V position “protons” from which protons J are removed. A free base can proton with ¥ proton (0 (b) salt 2 lithium; 0 (c) magnesium salt; or (d) an anion treated with a mono- or disilyl and within the scope of this invention is the use of a ligand of this invention for the preparation of a complex metal compound of this invention; to prepare for the production of a complex metallic compound including zy from the periodic table of elements; The lateanides 1" on a metal from one of the groups " to ©

jigands to; ligands 1; It is the actinides or actinides lanthanides of this invention in different forms; Including salts; ligands, and ligands that have different groups attached to them at position 7 may be used in preparation leading to compounds from Table 176-71. The metal is from the two groups Led metal complexe. ; in which there are from one to four of these periodic lanthanides or lanthanides vo dir

1 Not the ligands ¢ alone or in combination with other ligands; In a complex metal compound ¢ the methods of preparation may be similar or analogous to those discussed here for metal compounds of the group; the complex subject matter of the present invention; In addition to the various other preparation methods known in the field. Complex metallic compounds are useful as catalysts in various reactions; Including olefin polymerization reactions - and clearly; The naming of these complex metallic compounds is; In addition to the diverse neutral ligands and intermediates complex and challenging; Rules appear in the various systems of those names. Therefore; It is recommended to refer to synthetic representations. And in general; Concerning the bonding by the bridged bond of a complex compound having the geometric form fade. A complex of M-dihydrogen is bridged at position 1- ; Thus, the offending atom is in the position of Ym. The synthetic representations here must not give a strict literal interpretation as to degrees of links; Link lengths or strength. and for example ; The X-ray data show that the N-Cp bonds of some complex compounds are shorter than would be expected for a single bond; This is especially true for at least one double bond in the N-Cp bond. Vo and if then using ligands in complex compounds with a link of 1 8 oda where there is no bridge bond; In these cases, the offending atom may be mentioned as being in position 0- . Within the scope of the previous discussion on ligands, “The ligands of this invention correspond to the formula: B x+y+)-2 3 I L. A) where X equals zero or y 6 1 equals zero or \ 7 equals zero or xX +Y ¢ 1 equals zero or 1− XH Z equals zero or 1 ; Other symbols are defined as above; where the circle includes the region within the Cp loop the various probabilities of the bond property

YY

According to aromatic ¢ the property of a partial double bond or the aromatic property

Zaye X for convenience; Depending on the values of the concomitant stimulant or sling, the complex compounds are made catalytically effective by the union by using activation technology. Activating co-warming agents suitable for use herein include polymeric or ligomeric (reduced) allumaxans and in particular 0-methylalumoxane or triisobutylaluminum-modified methylalumoxane or isobutylalumoxane; acids; Particularly the Cras compounds substituted with hydrocarbyl 1” compounds of the group Jia Lewis; tri(hydrocarbyl) aluminum or tri(hydrocarbyl) boron and halogenated derivatives thereof One carbon atom in each hydrocarbyl group 11 to 1 (including super halogenated); It contains from above; ips tid (Nl) boron (Nl) or halogenated hydrocarbyl ¢ and in particular tri-0 compounds and more specifically tri-(ortho-phanofluorodiphenyl)borane and phase polymeric compounds; compatible and non-coordinating ( including the use of these compounds under oxidation conditions) and in particular the use of ammonium salts; phosphonium, oxonium, carbium, and cellulium asymmetrical; DL for the appropriate anions; asymmetric or iron salts and anions (after); and combinations of catalysts Lad electrolysis (discussed in more detail) 1 and associated and previous doping techniques. Different catalysts for metal complexe doping and previous doping techniques have already been studied for complex metal compounds.

VOY (NOV) following references: EP-A-7<; 277 US Patent No. (equivalent to ETA (equivalent to US Patent ETA (10 = ©) EP 24 AY 0 (equivalent to Patent 777 071 European Patent A-17/549 VIA with serial number YL

OF + 29777 ; and the European Patent 17 AYE (TTA) U.S. with serial number V49Y (filed in May) “VAAL (ATT) (equivalent to the U.S. Patent with serial number. The contents of which are incorporated herein by reference). The united groups are from neutral Lewis acids, especially the united Yo groups consisting of a tri-alkyl aluminum compound that has from 1 to; carbon atoms in each alkyl group and a tri-(hydrocarbyl) halogenated boron having from 1 to 71 carbon atoms in each hydrocarbyl group, “particularly tri(pentafluorophenyl)borane, Ko!.

yy (Otho-nanofluorodiphenyl)borane ¢ other conjugated groups of Lewis acid mixtures neutral with polymeric or oligomeric alumexanes; and conjugates of one neutral Lewis acid; in particular, tri(perfluorophenyl)borane with polymeric or oligomeric alumexanes are particularly desirable activating co-warming agents. A benefit according to this invention is the finding that the most efficient catalytic activation using that combined group of a mixture of tri(PF)borane/alumoxane occurs at low levels of 4:4 alumoxane. The molecular ratio of a touch of a complex metal compound ranges from the group; The most preferred © 1:20 to 1:1:1 tri(pentafluorphenyl)borane:alumoxane allows surprisingly effective use at low levels. 5:1 to 1,9:1:1 by means of this invention producing alumoxane olefinic polymers from alumoxane 0 with high catalytic efficiencies by using less amount of catalyst associated with olefin polymerizations having lower percentages of polymers composed of alumoxane. And also ; Polymers and thus larger metals were obtained. ¢ aluminum A precipitate of aluminum comprising suitable iron-forming compounds useful as co-catalysts in an embodiment of the present invention on a cation which is a Brønsted acid which can confer ve; an asymmetric anion; a . and as used herein; The term “no protons” means an anion or a substance that is either not coordinately linked to the initial complex compound containing “ls metal from the group”; and the catalytic derivative derived from it; Or, which binds symmetrically only weakly to those complex compounds and thus remains sufficiently susceptible to substitution by a neutral Lewis base. Yo is a cationic metal complex that does not transfer as an anionic substitute or part of it to the aforementioned cation, thus forming neutral complexes. That tube can work on balance. The components shall combine the charge of the active hot species (the metal cation) that has been formed and also the mentioned tube shall be sufficiently susceptible to substitution by compounds 1 and unsaturated acetylenes or other neutral Lewis bases m olefinic olefins; bi-olefin

7 p. ethers or nitrites. Suitable metals include; but without specifying; on aluminium; Gold and platinum. Suitable metalloids include; but without specifying; on boron; phosphorus sim sill; And silicon silicon. Compounds containing anions, which include coherence complexes containing one atom of a single metalloid, are of course well known; and be many; In particular, those compounds containing one boron atom in the anionic part 6 are commercially available. Such catalysts may be preferably represented by the following general formula: (L*_H)d(A) in which 0 is a neutral Lewis base; Bronsted acid; is an asymmetric anion ¢ with an integer charge ranging from 1 to ? More specifically, Ve pads are boron or aluminium in the original oxidation state, selected separately for each occurrence of hydride, di-alkyl derivatives, and hydrocarbyls; hydrocarbyl oxide, halo-substituted hydrocarbyl and halo-substituted hydrocarbyloxy; Substituted hydrocarbyl silyl. Bhalo (includes perhalogen-treated hydrocarbyl moieties, perhalogen-treated hydrocarpyloxi (per-halogen), and silylcarbyls (per-halogen); the © mentioned in it up to Yo is a carbon atom provided that Led is a halide © in not more than once Examples of appropriate © hydrocarpyloxide groups are shown in US Patent No. 74976477© the contents of which are incorporated herein by reference.

vo in a more granular resolution is 1 = l ; That is, the anti-ion has a negative charge, and the activating conjugated warming agents may be represented, which include . A- singular and be, which is particularly useful in the preparation of catalysts, the subject of this boron: invention by the following general formula (1*-17( (BOs); ° in which: * A is as previously defined; a native oxidation; and Ala in boron for boron isle B is a hydrocarbyl, hydrocarbyloxy, fluorinated hydrocarbyl or ©hydrocarbyloxy fluorinated; or its fluorinated hydrocarbyl silyl group 0 is a non-hydrogen atom; provided that in no more than one case 0 is 01 up to the hydrocarbyl. It is most preferred that © in each occurrence be a fluorinated aryl group; and in particular a pentafluorophenyl group . Compounds that make up iron AB and illustrative examples are, but without limitation, on Vo

Jal gall is used in activating a8 protons that grant Leas protons that include activating associated warming cations when preparing the catalysts the subject of this invention is: trimethylammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, Y. triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate,

yi methyltetradecyloctadecylmonium tetraphenylborate,

N,N-dimethylanilinium tetraphenylborate,

N,N-diethylanilinium tetraphenylborate,

N,N-dimethyl(2,4,6-trimethylanilinium)tetraphenylborate, trimethylammonium tetrakis(penta-fluorophenyl)borate, ° triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl )borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,

N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, 1

N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,

N,N-dimethyl(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, \o tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, dimethyl(t-butyl)ammonium tetrakis(2,3 ,4,6-tetrafluorophenyl)borate,

N,N-dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

N,N-diethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate, and

N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl) borate. XY.

Dialkyl ammonium salts such as: di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, and dicyclohexylammonium tetrakis(pentafluorophenyl)borate.

Tri-substituted phosphonium salts such as: triphenylphosphonium tetrakis(pentafluorophenyl)borate, Yo tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate, and vy tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate. It is preferable to find salts of tetrafluorophenyl (pentafluorophenyl) monoammonium from complex compounds of ammonium tetrakis (pentafluorophenyl) borate chain; Particularly complex compounds of alkyl and disubstituted alkyl ammonium and in particular methyldi(octadecyl)ammonium borate ¢ C14-Cy9 alkyl ammonium 0 methyldi(octadecyl)ammonium (Jt) quaternary (Ghas Luer) and dimethyl borate ( Tetradecyl) quaternary ammonium tetrakis(pentafluorophenyl)borate methyld(tetradecyl)Jammonium (— s— 1B pu— 3). Fluoro No Re » No Ry tri(pentafluorophenyl) borane and borates separately at each occurrence are N- Ry hydrocarbyl groups; N- Ry where (J: (Ri + (CéHs OH) ) B (Cs Fs)" to +4 carbon atoms and 1 substituted or unsubstituted with them from each occurrence of Ry and Ry; where (Ry R; 111701:) + B (Cs Fs) — 4 (R (Ro) NHCH3) 11 apart are saturated hydrocarbyl groups substituted or unsubstituted with C 1.01 to include an activated co-catalyst that forms another suitable ion on the oxidizing agent salt : cation and asymmetric matching anion represented by the formula (OXe+H)L(Ad)e in which Ave ¢ et is a cationic oxidizing agent with an OXe + charge to ? ; And 1 mh is an integer of . And L is as defined above Ad- 'Ya.

Ya

cationic oxidizing ferrocinium. Examples of cationic oxidizing agents include. 002 + or Ag+ librecorde HB; ferrocenium (substituted ferrocenium) are those anions previously defined in relation to AG agents) and the preferred embodiments are the activated hot conjugates containing a Brönsted acid; In particular, tetrakis(pentafluorophenyl)borate (pentafluorophenyl)© is another suitable activator conjugate that forms an anion on a compound that is lia and includes: a salt of a chlorbenium ion and a matching asymmetric anion represented by the formula ©*+; And Ciao is a carbinium anion© * is as defined above. The preferred carbenium ion is a tertyl cation; eg AY 0 0 terphenylmethylium acts to form an ion on a compound that is AT and includes a suitable activating catalyst or conjugate: a silylium ion salt and a suitable asymmetric anion represented by the formula Si (X') is the ld that ve and his are as previously defined. ¢ X! and ¢ Cryo is a hydrocarbyl© and the preferred activating co-warming agents of the psyllium salt are tetrafluorophenyltrimethylsilylium and tetrafluoroquinoleethylsilylium tetrafluoroborate. and ether-substituted addition products, and I have shown a / psyllium salt, in general, previously in

J.Chem Soc. Chem. Comm., 1993.181-384, F

Ya 0 Lambert, J.B., et al., Organometallics, 1994, 13, 2430-2443 In addition to the previous use of psyllium salts as activating warming agents for polymerization "Silylium Cationic" is mentioned in addition to the US patent application entitled Deposited in the names of Polymerzation Activators For Metallocene Complexes",

David Neithamer, David Devore, Robert Lapointe and Robert Mussell on Sept. 12,1994. 0 Certain complex compounds consisting of β-mercaptans, silos, and oximes with tri(PFP)porane are also effective catalytic stimulants and may be used in accordance with the present invention. These associated catalysts are described in US Patent No. 477; 1956; ©; The contents of which are listed here by reference. 0 Electrolysis on electrochemical oxidation of a complex metallic compound under AED and including conditions for electrolysis in the presence of a supported electrolyte containing an inert anion; Don't get along. And in technology; solvents are used; Supported electrolytes and electrolytic potentials so that the by-products of electrolysis will render the complex metallic compound inactive. Catalytically they are not completely formed during the reaction vo and more specifically; Suitable solvents are substances that are: liquids under m); Can dissolve 001 under conditions of electrolysis (temperatures generally from zero to supported electrolyte); and is inert. “Inert solvents” are those that are not reduced or oxidized under the reaction conditions used for electrolysis. It is generally possible Supported CulSl General In light of the desired electrolysis reaction Choose a Yo solvent that is not affected by the voltage used for the desired electrolysis Solvents; DME mixtures of choice include difluorobenzene (all isomers) Dimethoxyethane, of which the electrolysis may take place in an electrolytic cell containing an anode and a cathode (also referred to as the working electrolyte and counterelectrode, respectively).

Ae the cell we find glass-plastic; Ceramics and metal. Covered with glass. The electrodes are prepared from inert conductive materials, by which we mean the conductive materials that are not affected by the reaction mixture or reaction conditions. And platinum or palladium is a preferred inert conductive material. Normally, an ion-permeable membrane works, for example: a displacement mixture (calcined mixture) of micro-fractional glass separates the cell into separate chambers; The treating electrode chamber 0 and the offending electrode chamber. The treated electrode is immersed in a reaction medium that contains a complex metallic compound to be activated. solvent; cementation electrolyte; And any other desirable materials to mediate the electrolysis or stability of the resulting complex. The offending electrode is immersed in a mixture of the solvent and the supported electrolyte. The desired voltage may be set by theoretical calculations or experimentally by scanning the cell with a reference electrode such as 0 set back cell current; Lad drew a silver electrode that was immersed in the cell electrolyte. The current is carried out in the absence of the desired electrolyte. Electrolysis is completed when the current drops from the desired level to the background level. In this way ; can. It is easy to detect the complete transformation of the primary complex metal compound, and the appropriate support electrolytes are salts containing a Vo cation, and the preferred support electrolytes are salts. An anion; inconsistent ;: in which. GTA analog formulas are a cation that is inactive towards the starter and the resulting complex; and GT. are as defined A on GF-substituted ammonium or phosphonium cations and examples of Ye cations include a non-hydrogen atom. The preferred cations are 0 tetrahydrocarbyl in which up to 0 tetrahydrocarbyl cations (butyl ammonium) and tetraethylammonium and during the activation of the complex compounds subject of this invention by electrolysis is the cation of the supported electrolyte which passes to the counter electrode and is transferred M to the treated electrode to become the anion of the resulting oxidized product. Either the solvent or the Yo cation is reduced

A

of the electrolyte supported at the counter electrode with a gram molecular amount equal to the amount of the complex compound of the oxidized metal formed at the working electrode. The preferred fortified electrolytes are tetrahydrocarbyl ammonium salts of borates with carbon atoms in each hydrocarbyl group 10 to 1 quaternary (perfluorouryl) of or perfluorouryl; In particular, tetra(butylammonium) quaternary 0 (petafluorophenyl) borate. Another recently discovered electrochemical technique for the production of activated cocatalysts is the electrolysis of disisilane in the presence of a non-coordinate mallam anion source. . This technology is explained more and is mentioned in the US patent application referred to, “Silylium Cationic Polymerzation Activators For previously referred to and which they sold 0 filed on Sep. 12, 1994 Metallocene Complexes”, and it may also use the previous electrochemical activation technology and associated catalysts In particular, it is a mixture of a third compound, Junie, activated by union together, and there is a third union (hydrocarbyl) boran, tri(hydrocarbyl)aluminum, to carbon atoms in each hydrocarbyl group with 1 in it. Of trihydrocarbyl borane 0 or polymeric. oligomeric alumoxane or ligomeric compound The molecular ratio of the used catalyst/cocatalyst ranges from about 0:01 to 000:1 and most preferably from 1:001 to 1:0001 is preferred than alumoxane is used; when used by itself as an agent 1:1 to 1:0001 and better than at least double the amount of compound 001 in a large amount; generally catia Co-catalyst © Complex metal on a molecular basis Tri(PFP)borane is used when used as a catalyst or co-activator in a gram molecular ratio to the complex metal compound 1:1 to 6:1; better than 1:1; The most preferred from 1:01 to 1 10.0 range from and the remaining activated co-catalysts are generally used in an amount of . 1:© to . Approximately equivalent (equal) gram molecular weights to the complex metal compound Yo P

AY

The process may be used for the polymerization of unsaturated ethylene monomers of which? to 01 carbon atoms. Either alone or in combination together. Preferred monomers include aromatic monomers of monovinylidene; In particular styrene, 4-vinylcyclohexene, 4-vinylcyclohexene, phenylcyclohexane 0, norbrnadiene, and aliphatic wen (alpha-olefins) in particular ethylene, propylene, and isopropylene isobutylene, 1-butene, 1-pentene, 1-pentene, 1-hexene, 1-methyl-1-pentene, 3-methyl-1- pentene and 4--0- Jefe 4-methyl-1-pentene and -1-heptene 1-heptene and 1-actene 1-octene and dienes sold; and mixtures thereof. The most preferred monomers are ethene, rubylene, 1-butene, 1-hexene, 1-octene, mixtures of ethylene, propylene, and unconjugated dienes, particularly norbornene ethylene. In general, polymerization may occur under well-known conditions. In the previous field for Ziegler-Natta or polymerization reactions of the type Kaminsky-Sinn; that is, temperatures of No range from zero-cp YOu and preferably Ve to 1007C and pressures from atmospheric pressure to 00 pressure Aerial It may be used to polymerize the powder in the presence of a suspension; solution; paste 0 gas phase; bulk and in a solid state or other condition if desired. a prop material may be used; in particular silica; alumina; or as a polymer (in particular poly(tetrafluoroethylene) or polyolefin). It is used desirable when the catalysts are used in a gas phase polymerization process or in putties. It is preferable to use the support in an amount that gives a weight ratio of the catalyst (depending on the metal): The support is from 1:000,000 to 1:01, and the most preferred is from 1:0,000 to 700:1, and the most preferable is from 0,000:000. :1 to Fe:1. One of these polymerization processes includes: contact; optionally in a solvent; one or more of the Lill-olefins aeolefins with H or Yo according to the present invention; in one or more continuous stirred tank or tubular reactors; connected in series or parallel or in the absence of a solvent; optionally in a fluidized bed gas phase reactor; and extract the resulting polymer. And he has

AY

Addition of the condensed monomer or solvent to the gas-phase reactor (LS) is well known in the art. In most polymerization reactions, the molecular ratio of the catalyst: the polymerizable compounds used ranges from 1 TY to 1 TY; and most preferred by

AMY

The solvents suitable for polymerization are inert liquids. BY) includes straight and branched chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; cyclohexane, aliphatic hydrocarbons, cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptan 0, and mixtures thereof; and hydrocarbons treated with perfluorinating, such as the Copp alkanes treated with perfluorinated; and the like, and aromatic compounds and aromatic compounds substituted by alkyl such as benzene, toluene, xylene, ethylbenzene, etc. Solvents also form liquid olefins that may act as monomers or Vo-associated monomers that include ethylene, propylene, butadiene, and 1-butene Cyclopentene, 1-hexane, 1-heptene, and;-phenylcyclohexene Judy cyclohexane Vy-methyl-1-pentene and;-methyl-1-pentene, 10-,-hexadiene, 1- octane, 1-decene, styrene, and diphenylbenzene; allylbenzene and phenyltoluene (including in and around all isomers or in a mixture); And the like. The above will also be suitable for you. 7 Preservation systems may be used, or in combination with at least one homogeneous or heterogeneous additional preservative or polymerization, in separate treatments, respectively, or in combination to prepare polymeric partitions with desirable properties. An example of that process is shown in International Patent 44/5086; which is equivalent to US Patent Serial No. 770 17/904; In addition to the US Patent Serial No. 18/0988 filed with YA January VAY the contents of which are incorporated herein. For reference Yo

Af By using the warmed systems subject of this invention, it is possible to easily prepare mixed polymers having a large proportion of the conjugate monomer and, accordingly, a low density and a low melting coefficient. any ; High molecular weight polymers are easily obtained by using these catalysts even at high reactor temperatures. This result is highly desirable because the molecular weight of the blended *-olefins polymers can be easily reduced by the use of hydrogen or a similar chain-reducing agent; In any case, the increase in the partial weight of the copolymers (mixed) of * - alpha olefin. Normally it can only be obtained by reducing the polymerization temperature of the reactor Operating a polymerization reactor at fairly low temperatures (Junin) does not significantly increase the operating cost since the heat must be removed from the reactor To maintain the 0 reaction temperature low, while at the same time heat must be added to the benzene stream the Jil reactor is increased to work on evaporating the solvent.In addition, throughput due to improved solubility of the polymer, lower viscosity of the solution and concentration By using these catalysts, homogeneous polymers of ©-olefin and blended polymers with densities ranging from 6.80 g Vo 0001 to 0.5001 to 0.97 g/cm are easily obtained. Molten flow rates ranging from 0 dci/g/min in a high-temperature process, and catalyst systems, the subject of this invention, are particularly preferred for the production of homogeneous polymers of ethylene and blended polymers of ethylene/alpha olefin. The use of warm systems, the subject matter of this invention, in continuous polymerization processes and in particular © in solution polymerization processes; persistent; with high reactor temperatures that encourage the formation of nami; Thus, polymer chains of vinyl-terminated polymers that may be introduced into a polymer that gives a long-chain branching. The use of this system of catalysts, preferably olefins having a potential of X =, allows the economical production of copolymers of high free ethylene Gal in operation similar to the amount of low density ethylene produced by Yo compression.

Ao and in another aspect of the processes subject of this invention; There is a preferred process that includes polymerization of olefins by polymerization of the solution in the paste phase to polymerize the olefins under polymerization conditions with a special catalytic system Cog = X olefins and one or more of the most preferred reactions. 4 You C to about 001 C with this invention at a temperature ranging from The range of temperatures for this process is the temperature ranging from about 0 C to 91 C degrees ranging from about Lad C; The most preferred is 001 to about 000 m / m. improved operability by polymerization of ethylene alone or mixtures of ethylene 001 to about ¢ olefins with lower proportions of diene-induced “[1]” discharge; as norbonaraine X-octadine; A1-4- Decadiene. The unique combination of high temperature -7 > 1 A high molecular weight (low melting coefficients) at high reactor temperatures 0 and high reactivity of the conjugate monomer preferably allows for the economical production of polymers that have hydrated physical properties and excellent workability It is preferable to include those containing ethylene; and a conjugated monomer with a branched Coa =X olefin on the polymers. These polymers are produced in a solution process; And the most preferred of > is preferred. 7 continuous solution process. as an alternative; These polymers may be produced in a paste gas phase 1 process. lee or gas phase As previously mentioned; This catalytic system is particularly useful in the preparation of high productivity and yield. The process may be EPDM and EP mixed polymers used in either a solution or paste process, each of which is known in the field. The use of a catalyst system from a bis Kaminsky, J.

Poly.

Sci, 701.23, PP. 2151-64 (1985). Y-(cyclodiethylene) zirconium dimethylalumoxane soluble in solution polymerization of plastics CEVA polymerization process © YYA CEVA US Patent No. EPDM and EP 43 have shown yall phase putty using similar retention systems It is based on bis (cyclopentadienyl) zirconium.In general, it is desirable to produce those for elastomeric consisting of Yo under conditions of increased activity of the monomer component consisting of diene. in the following way; which is still correct despite EVA's explanation of why it is so patent

One of the developments that have been reached in this matter, and there is a major factor affecting production costs and then the use of EPDM is the cost of the monomer consisting of diene-0, and diene is a monomeric material that is more expensive than ethylene or propylene-0 and also ; The activity of diene monomers with previously known metallocene catalysts is 0 less than that of ethylene and propylene. As a result ; To achieve the required Aa from introducing dienes to produce EPDM with an acceptable faster curing rate; It was necessary to use a concentration of the diene monomer; which die is expressed as a percentage of the total concentration of monomers present; With a significant increase compared to the percentage of diene desired to be included in the final EPDM product.

01 Since large quantities of unreacted diene monomer must be extracted from the polymerization reactor stream for recirculation, the cost of production is unnecessarily increased.

Another plus to the cost of producing EPDM is the fact that; generally; Lead

The catalyst for olefin polymerization was exposed to a diene »in particular

ve high concentrations of aluminum diene monomer to produce the required ratios of diene inclusion in the final EPDM product” often reduces the rate of activity at which the catalyst will cause the polymerization of ethylene and propylene monomers to occur. correspondingly; it

Lower production rates and longer reaction opacity are required - compared to the production of And soft ethylene-propylene copolymer or other soft-copolymer

© Musaheb (Mukhallat) by Alpha-Olefin.

| This catalyst system allows in a detailed manner an increased efficiency of the dienes and thus prepares EPDM polymers with yield and yield of le . The catalyst systems subject of the present invention also achieve economical production of EPDM polymer with diene proportions of 01 wt percent or greater; These polymers have desirable faster rates of curing.

Yo can a; The unconjugated diene monomer is a straight-chain cyclic hydrocarbon diene; unload the chain or loop it from -

AY

carbon atom. Among the examples of suitable unconjugated dienes, we find 11 to 1 about K 1,4-hexadiene hexadiene - 1-chain derived noncyclic dienes, for example; ;;; Branched-chain noncyclic dienes e.g. 0- methyl-1,6-0ctadiene 1-octadiene = A= dimethyl-diene = 1 and S-methyl-1,4-hexadiene -1 ¢ -; YN = J 30a -1; f 3 7-dimethyl-1,7-octadieene and mixed isomers of the second 3,7-dimethyl-1,6-octadieene; aliphatic diene dihydroocinene and dihydrocynene dihydromyricene hydromyrcine-1; 4 1,3-cyclopentadiene cyclo-1 ¢ ¥ Na monocyclic 1,5-cyclooctadiene cyclo-1 ; E 1,4-cyclohexadiene cyclohexadiene; and the aliphatic polycyclic dienes 1,5-cyclododecadiene (1,5-cyclododecadiene =) 04 0 combined and cross-linked rings such as cyclic aliphatic tetrahydrododecadiene - (1,1 1) - and tetrahydromethyl and dipenta bicyclo-(2,2,1)-hepta-2, 5-diene ?- diene © — Lia

Sa from alkylidene norbornenes, cycloalkenyl norbornenes and alkylidene ~06 4 ¢ (NN?) 5-methylene-2-norbornene O——— ys -?- pa —0 yo

Y= and ©- isopropenyl 5-propenyl-2-norbornene propentyl -?- norbornene

TY (cyclopentenyl)-7-norborene and *-cyclohexilidine -4) oy norbornene Norbornene and *-phenyl-7-norbornene One of the dienes typically used is (HD) 1-hexadiene dienes form Particularly preferred are the 4;" EPDMs for the preparation of 8-(VNB)vinylidene-7-norbornene —0 4 (ENB) ethylidene-7-norbornene —0,0 (DCPD) cyclopentadienyldipentadienyl (MNB) methylene-7-norbornene, of which the dienes of particular preference are 0- ethylidene-?-norbornene (HD) 1-, 4-hexadiene; (ENB) S-isopropylidene-2-norbornene wt 900 to about 10% preferred to approx EPDM and elastomers may contain up to 5+ wt in hydroethylene or more Te of ethylene; most preferably about HL ve preferably about © to about 80 Weight percent of ethylene.‎

AA

IL suitable for use in the preparation of seolefins, preferably alpha-olefins and f. And from flexible avolefing by means of ethylene and dienes are these alpha-olefins, we find propylene acolefing unlimited illustrative examples on alpha-olefins -1, pentene, 1- heptene, 1-butene, 1-pentene, 1-hexene and; ?- methyl V propylene in acolefin octene 1-decene 1-dodecene . The alpha-olefin © wt% is generally included; Most preferred at Ar to about 10 count is EPDM polymer to about 10 wt. Unconjugated dienes Ye are generally introduced by about weight per cent; and most preferred at about 10 to about 1.5 at about EPDM in weight percent. and at VY weight percent; and most preferred at about 11 to 1 ENB Desire; More than one diene may be introduced at the same time eg 110, _ 0: The total diene induction shall be within the limits specified above. The catalyst system may be prepared as a homogeneous catalyst by the required components into a solvent where the polymerization will take place by polymerization in solution. The catalyst system may also be prepared and used as a heterogeneous catalyst by adsorbing or adsorbing the required components on the Catalyst support material such as silica gel ¢ alumina or other suitable inorganic support material 1. and when preparing in a non-homogeneous or fortified form; It is preferable to use silica as a backing material, and inorganic backing materials may be treated; For example, for example; silica; with alkyl. Ammonium or other agents of the chemical technique to reduce the percentage of hydroxyl on the surface of the gas support, and the heterogeneous form of the catalyst system may be used in the polymerization in the gas phase or in the putty. and as a practical definition; The polymerization of the putty takes place in phase © liquid diluents, preferably; The Lalas diluent is under conditions in which the insoluble polymerization product of putty polymerization is one or more hydrocarbons that have fewer than carbon atoms. and at will; saturated hydrocarbons such as ethane may be used; Propane 0 olefin or X = or in part as a diluent. Similarly a different LS monomer or butane olefin may be used as a diluent. Most preferably, the dilute in —X includes a mixture of vo monomers. Olivine or monomers to be polymerized = X major part at least monomer A ;

The preservation system or the subject matter of this invention may include an organometallic component of aluminum that includes alumoxate, alkyl ammonium or a combination thereof. This component may be present in an unactivated amount and act mainly as a scavenging agent  or it may interact with a catalyst or an associated component. To increase the effectiveness of the warming component; Or he may perform both functions

° It is understood by the appropriate functional group on the catalyst, catalyst, or concomitant of the catalyst system, or can be covalently or ionically bound to the support material of the catalytic component; Which includes a support material that is a non-metal halide oxide polymer or a mixture thereof.

The preferred supports for use in the present invention include types of selecomalites

0 porosity; blame us; alumino silicone; and mixtures thereof. The backing material is most preferred

It is silica and the support material may be in granular form; lumpy spherical; or any

other physical form and including appropriate materials; but without specifying; on available silica from

SD 2316.30, Davison under the names Geace Davison (division of W.R.

Grace & CO)

Syoid 245, Davison 948 and Davison 952, and from Cros Field under the name EST0 ¢ and from

Degussa AG Vo under the name 812 Aerosil; Alumina is available from Akzo Chemical Inc. under the name Ketzen Grode B.

It is preferable that the supports suitable for this invention have a surface area as lined

By measuring the nitrogen porosity using the BET method from 01 to about

paf¥a 0; Preferably from about 001 to 100 m 7 / gm; The pore size ranges

© to the abutment; As determined by nitrogen adsorption; preferably between 0.1 and #cm7/g ; Preferably from about 1.7 to 7" cm/g. The particle medium depends on the process used; but preferably in the range from 00 to One µm; preferably 1 to 100 µm.

Both silica and alumina are known to inherently contain small amounts of the hydroxyl functional group, Yo. and when used as a prop here; These materials are preferably subjected to heat treatment or chemical treatment to reduce fa 8

hydroxyl in it. Residual heat treatments are carried out at a temperature of 1°C to 0°C (preferably 0051°C to a Ave for ½ hours or greater) for a period of 10 minutes to 0* hours in an inert atmosphere or under reduced pressure. Aad pal chemical treatments include reaction with alkylating agents of Lewis acid Jia trihydrocarbyl 0aluminium compounds, trihydrocarbylchlorosilane compounds and trihydrocarbyl alkoxysilane compounds A; similar factors. The remaining hydroxyl groups are then denatured by a functional group may be introduced into the support by a silane or a chlorosilane functionalist to bind to the silane suspension = (Si-R) = ; or chlorosilane = ((0:8) = , where R 0 is a hydrocarbyl group©. The appropriate functional group introduction agents are compounds that react with the two hydroxic groups present on the surface of the support or react with the silion or aluminum for the interlayer. Examples of suitable functional group introducing agents include ihsilane, hexamethyldisilane, diphenylsilane, methylphenylsilane, dimethylsilane, dimethylsilane, and dichlorosilane;1_dichlorodimethylsilane. Pre-functionalized silica alumina compounds in US Patent No. 9750 5897” or GAYA (FTA 2) – the contents of which are incorporated herein by reference. The support may also be treated with an aluminum component selected from alumoxane or an aluminum compound of formula 77 AIRY! 'R?n' where RY is separate at each occurrence of which is © is a hydridesk or ©; R2 is a hydride » 8 or SOR 3 is JY or is not a zero or a 1 duals is plural of 8 or not equal to *. BY groups of !8 and 82 include methyl, methoxy, ethyl, ethox, propyl (all isomers), and propox (all isomers); butyl (J) isomers); and Biotox (all isomers); Phenyl, Fenox, Benzel and Benzelox. the best; That the aluminum Y component be selected from the group consisting of aluminoxanes and trihydrocarbyl (Cra) aluminum compounds. Among the most preferred aluminum components are aluminoxanes, trimethylaluminium, triethylaluminium isobutylaluminium and mixtures thereof. and

Omoxanes (also referred to as aminoxanes) are oligomeric or polymeric aluminum oxycompounds containing exchanged chains of aluminum and oxygen atoms; Thus, aluminum carries an alternative; Alkyl group is preferred. It is believed that oxygen; for alumoxane (Al (R) - OY) The structure of alumoxane can be represented by the following formula is as previously defined R ; for a linear compound; where RAL OF AL R (- 0) is cyclo ¢ and to 0 preferably at least 0; and as 1 and /n’ is an integer ranging from typical aluminoxanes are the products of the reaction of water and alkyl aluminum Which, in addition to an alkyl group, may contain halide or alkoxide groups, and produces several different aluminum reactions, for example, trimethylaluminium JST compounds, and triisobutylaluminium, with water, so-called modified aluminoxanes or Mixture 0 and the preferred inmoxanes are methyl inmoxane and a modified methyl alumoxane, especially isobutyl and Coy in small amounts of alkyl aluminoxane groups generally contain small to large amounts of alkyl aluminum compound. Techniques for the preparation of aluminoxane-type compounds by contacting an alkyl aluminum compound with an inorganic salt containing water per milliliter per US Pat. Or another substance This is indicated by Sia a substance containing water that can be reproduced in EP 6044 378 -a - and then alumoxane d is introduced into the advertisement by the reaction of alumina or hydrated silica; whose functional group has been inserted, optionally with silanes or osiloxanes and hydrocarbylsilanes or chlorosilane groups with aluminum according to known techniques. And for studies, (Cio) JS) is a triple compound

ASS Patents and previous publications are listed here; or US patent applications. The analogue herein is by reference and includes treatment of the support material with the purpose that it also includes optional charges of Yo alumoxane or trialkyl aluminum on contact before; After or at the same time with the addition of the complex compound or the preservation or hereinafter with the alumoxane A tri-alkyl aluminum compound + and as

especially triethylaluminium or triisobutylaluminium + and optionally the mixture may also be heated under an inert atmosphere for a period and at a temperature sufficient to stabilize the alumoxane and tri-alkyl aluminium; The complex composite or bulwark system. optionally; The stent component may be exposed. whose content of alumoxane or trialkyl aluminum compound 0 has been treated to one or more washing steps of unsubstantiated alumoxane or trialkyl aluminium. Besides contacting the support with the alumoxane, the alumoxane may be produced in situ by contacting silica or non-hydrolysed alumina or hydrated silica or alumina with optionally a tri-alkyl ammonium compound in the presence of an inert diluent. This process is well known 0 in the art; And it was shown in the European patent - A - 100 You in the American patent No. DLA ANY 4; and 8 178 ©; Studies for which or for the US BLA application are listed here by reference. Suitable aliphatic hydrocarbon thinners include pentate, isopentate, hexane, heptane, octane, isooctane, nonane, isonone, decane, cyclohexane, methylcyclohexane, and combined groups of two 1 or more such diluents. The corresponding aromatic hydrocarbon diluents are benzene, toluene and xylene compounds and other alkyl or aromatic substituted with halogen 0 and the most preferred; that the diluent be an aromatic hydrocarbon; Especially toluene. After preparation in the foregoing method the hydroxyl residue thereof is desirably reduced to ratios of less than 10 mequivalents of 011 per gram of support by any of the aforementioned techniques 0 and the associated warming agents of the invention Lind may be used in combination with an aluminum tri(hydrocarbyl) having from 1 to 0 carbon atoms in each hydrocarbyl group” an alumoxane, ligomeric or polymeric compound; a di(hydrocarbyl) (hydrocarbilox) aluminum compound having from 1 to 10 carbon atoms in each hydrocarbyl group Ye or hydrocarpilox ; or a mixture of the above compounds; at will. These aluminum compounds are used to the advantage of being able to utilize them for the removal of impurities – oxygen – water and alohides from the polymerization mixture. The preferred 8 ay aluminum compounds, especially those in which the 0 aluminum Crs groups are composed of tri-alkyl compounds, are ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, neobenyl, or isobenyl; methylalumoxane; Modified methylalumoxane and the second gram isoform of the compound A al-butylalumoxane. It is preferable that the ratio range

0 aluminum to the metallic complex of 1:00001 to 1 ; Most preferred from 1:000 to 1:001 and Most preferred from 1/001 to 10:001.

And on the contrary; Solution polymerization occurs under conditions in which the diluent acts as a solvent in the components of the reaction; Especially with BP or EPDM polymers. Preferred solvents include mineral oils and various hydrocarbons that are liquid at

0 reaction temperatures. Examples of useful solvents for alkanes are methylpentane, isopentane, hexane, heptane, octane, and nonane; In addition to mixtures of alkanes including Kerosene and IsoparE™; key Exxon Chemical Inc.; True alkanes Jie cyclopentane and cyclohexane; Jie aromatic compounds: benzene, toluene, xylene, ethylbenzene, and 0-diethylbenzene.

Vo and at all times; Individual components as well as catalyst components must be protected from oxygen and moisture. Therefore; The catalyst components and catalysts must be prepared and extracted in an atmosphere free of oxygen and moisture. preferably; Therefore «that the two reactions take place in the presence of Gha or Gila; Inert eg + Pentrogen.

Y. And ethylene is added to the reaction vessel in an amount to maintain a variable pressure in an increase of the combined vapor pressure of the monomers » — olefin and diene. The proportion of ethylene present in the polymer is determined by the ratio of the differential pressure of ethylene to the total reactor pressure. In general the polymerization process is carried out by differential pressure of ethylene from about 01 to 001 psi (Ve to 7005 kPa); and most preferred by

Yo is about Er to about ¼ psi (Ve to Yer kPa). The polymerization is generally carried out at a temperature range from Yo to 0,000 °C; Preferably from 75 to

0 m; And the most preferred is from 96 to 4600 AD. Polymerization may take place in batches or continuously. preferably a continuous process; In which the catalyst 0 ethylene »-olefin and optionally the solvent and diene are supplied to the reaction zone from which the polymeric product is continuously removed. Within the scope of the terms “continuous” and “continuously” as used in this text are those processes in which there are intermittent additions of reactants and transformation of products at small regular intervals of time; Thus; passing by

time; The whole process is continuous. without limiting in any way the scope of the invention; There is a way to carry out this polymerization process as follows: In a stirred tank reactor the propylene monomer JAY is

0 continuous Lig with solvent; Diene monomer and ethylene monomer. The reactor contains a liquid phase consisting mainly of ethylene monomers; Propylene and Iine together with any additional solvent or diluent.

and upon return; A small amount of 11" release-causing ion may be added such as norbonadapine and Y=1 or katadiene or A=1 decadiane also 0

,. The catalyst and co-catalyst are continuously introduced into the liquid phase of the reactor 1 and the temperature and pressure of the reactor may be adjusted by adjusting the solvent/monomer ratio ¢ the rate of catalyst addition; In addition to compression by files; Cooling or heating covers or both.

The polymerization is controlled by the catalyst addition rate. The percentage of ethylene in a product is determined

© the polymer by the ratio of ethylene to propylene in the reactor; which are adjusted by manipulating the charge rates corresponding to those components to the reactor. And the partial weight of the resulting polymer is adjusted; Optionally by adjusting other polymerization parameters Jha temperature » monomer concentration; or by a stream of hydrogen then introduced into the reactor; Also known as hun in the field.

F

The reactor stream is contacted with a catalyst deactivating agent such as water. It is done optionally

heating of the polymer solution; The polymer products are extracted by evaporating ethylene and propylene

aqueous propylene plus a residual solvent or diluent at reduced pressure; and when necessary; Procedure for re-priming the volatile compounds in equipment such as an extruder for principalizing

© Volatile Compounds. In a continuous process, the average residence time of the catalyst and polymer in the reactor ranges from ½ minutes to ½ hours; Better than 10 minutes to > hours.

and in a preferred mode of operation; The polymerization is carried out in phase, or continuous polymerization in solution

It contains two faulty reactors in series or twin. In one of the reactors a product is formed

0 high partial weight (partial weight 700,000 to 10,000080; most preferably from Eee 0a to 000,000) while in the second reactor a low partial weight product is formed.

Relatively (partial weight from Onn to Force es) and the final product is a mixture of the two reactor streams that unite before the initialization of the volatile compounds to produce a homogeneous mixture of this double reactor process allows for the preparation of products that have improved properties. In a preferred embodiment, the The two reactors are connected in series, i.e. the conditions of the reactor are set so that the weight ratio of the polymer produced in the first reactor to that produced in the second reactor ranges from 80: Ye to 710: 80. In addition, the temperature of the second reactor is set to produce a product for it Lower molecular weight.This system is allowed on the way

© Useful for producing 27324 products that have a wide range of MOONEY viscosities as well as excellent toughness and excellent processability. The viscosity of MOONEY is set preferably

ASTM D 1646-94, ML1-1© (at YO 1 m) for product to be in the range 1 to

.011 to 01 and the most preferred out of 101 ; Preferably from 0 to 0 and the process subject of the invention can be used preferably for copolymerization in the gas phase polymerization of olefins and the gas phase processes are the Yo gas phase and in particular the homopolymerization and copolymerization ¢ olefins polymerization for olefins

for ethylene and propylene; the copolymerization of ethylene with higher alpha-olefins; For example “-1-butene, 1-hexene, and ;-methyl-1-pentene are well known in the field. High-density polyethylene (HDPE), medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE) and poly-propylene are used commercially on a large scale. The process uses the gas phase; eg “JB” type using a mechanically stirred bed bed or a gaseous bed bed as the polymerization reaction zone + preferably the process in which the polymerization reaction is carried out in a drum head polymerization reactor containing a liquid bed bed of polymer particles supported on a perforated plate ; liquefaction mesh By 0 agree a liquefied gas. The gas used to liquefy the bed contains the monomer or monomers to be polymerized; It also acts as a heat exchange media to remove the reaction heat from the bed layer. The hot gases exit from the top of the reactor; Normally by area ----; known as Lind in the throttle zone; It has a larger diameter than the fluid bed layer and where the fine particles that have been introduced into the gas stream have the opportunity to fall by the influence of gravity inside the bed layer. It may also be preferable to use a conical scalpel to aerate ultra-fine particles from the hot gas stream. The gas is then naturally recirculated back into the bed by a blower or compression unit and one or more heat exchangers to degas the heat of polymerization. Yes A preferred method of cooling the cradle layer ¢ in addition to cooling is by means of recirculating garrot coolant; They charge volatile liquid to the bed layer to give evaporative cooling effect; Often referred to as condensation operation. And the volatile liquid used in this case can be; For example; It is an inert, volatile liquid; For example ; A saturated hydrocarbon having about “ to about cA preferably; to + carbon atoms. Yo in which case the conjugate monomer itself is a volatile liquid ¢ or can be condensed to give that liquid » and can suitably be charged to the bed layer to give effect

Evaporative cooling Examples of olefin monomers that can be used in this method are olefins containing three to about Ald; Three to six carbon buttons are preferred; And the evaporation of the volatile liquid in the hot fluidized bed layer to form le mixed with the gas or liquefaction. and if the volatile liquid is a conjugate monomer ©; It will undergo part of the polymerization in the cot layer. The volatile liquid then exits the reactor as part of the hot circulation; The pressure unit enters the heat exchanger which is part of the recirculation loop and the gas is cooled or recirculated in the heat exchanger; And if the temperature to which the gas is cooled is less than the melting point; The liquid is precipitated from the gas and this liquid is recirculated as desired in a continuous manner to the fluidized bed. It is possible for the SL that was deposited to be recirculated to the bed layer as liquid droplets loaded into the Ga stream or recirculated. This type of operation shows; For example in European Patent 89,741; US Patent No. 47744©; ; INTERNATIONAL PATENT 94764496 and US Patent No. OFOYVER; which are included here by reference. A particularly preferred method is to recirculate the liquid 1 into the bed bed to separate the liquid from the recirculation gas stream and to return this liquid directly to the Jay; It is preferable to use a method that produces very small droplets of liquid in the cot layer. This type of process is described in BP Chemicals' International Patent No. 1,478,077; which are included here for reference. The polymerization reaction that takes place in the gaseous bed fluidized bed is prepared by the continuous or semi-continuous addition of the catalyst. This catalyst can be supported on an inorganic or organic support sala as indicated above. The catalyst may also be subjected to a prepolymerization step; For example ; By polymerization of a small amount of olefin monomer in a liquid inert diluent; To give a catalytic composition that includes catalyst particles incorporated into olefin polymer particles Yo. The polymer is produced directly in the catalytic bed layer by the catalytic copolymerization of the monomer and one or more monomers associated with the diluted particles of the catalyst; Support catalyst or prepolymer in the bed layer. which be.

A

preferably identical to the target polyolefin; preparation of the bed layer by drying the gases and any monomers prior to the introduction of the catalyst; nitrogen monomers or other Jala dilution nitrogen monomers that are desirable to be present in the recirculation gas stream; For example, or an inert gas for condensation when it is operated in nitrogen as a hydrogen chain transfer agent and the resulting polymer is discharged continuously or intermittently. gas phase A state of condensation of the gas phase o . of the fluid bed bed as desired. The gas-phase processes suitable for the conduct of the present invention are preferably continuous processes set up for the continuous supply of reactants to the reaction zone of the reactor and the removal of the products from the reaction zone of the reactor; Thus, it is set up. with the Joli reactor a large scale steady state medium in the region of 0 and preferably; The fluidized bed bed of the gaseous phase process is operated preferably from about 10°C to about 1000°C; 00 cp at temperatures greater than . 0011 M and most preferably from about 17 M to about preferably. The molecular ratio depends on the conjugate monomer Jo used in the polymerization on the desired density of the composition to be produced and it is about © or 1 less. and desirable; When producing materials with a density range from about +8 to about 0.47, the conjugate monomer to monomer ratio is less than 7; It is preferred that it is less than 0.0, and the most preferred is also less than 60.07 and it is less than 01. preferred; The ratio of hydrogen to monomer is less than about 8 ; of 0207 and may of ; the most preferred of 00+; Most preferred LY of preferred OF © . be less than 0.01 and the range values shown above for the process variables are suitable for the gas phase process subject of the invention and may be suitable for other processes that can be prepared to perform the gas phase of this invention.

The patents and patent applications show processes in the gas phase that may be prepared for use in the process subject of the invention; In particular ; US Patent No. 0¢ 40774 ¢ 057704 ¢ 07474; 4.0477; 001711145; 411,177; 674,171 m 1 AH; lamah) “to suffice ¢ OEVYY YA; OY bungalow; 6 and European international patent applications 1,899,777; 19785050 and international BCT requests 7447077; international 14,784,497; international 1,478,498; international 4,478,077; International 1016; international 447997497; International 4,807,447 that are included here by reference. catalysts may be used; whether or not supported by any of the previous methods; Polymerization of unsaturated monomers lf y ethylenically acetylenically with from 1 to 000001 carbon atoms either alone or in united dc gana monomers include Preferred over alpha — olefins, adi- olefins, especially ethylene: propylene, isobutylene, 1-butene, 1-0-pentene, l1-pentene, and - 1-hexene 1-methyl-1-pentene 3-methyl-1-pentene ¢— methyl-10-pentene 4-methyl-1-pentene and -1 1-octene and -1-decene 1-decene x: — long-chain large-molecule x-olefins and mixtures thereof the most desirable 5 monomers include styrene and alkyl-substituted styrene M © tetrafluoroethylene , vinylbenzocyclobutane 00 , ethylidenenorbornene , 4- hexadiene V4 1,4-hexadiene 7- 1,7-octadiene and phenylhexane vinylcyclohexane and ¢— Jicyclohexane 4-vinylcyclohexene and divinylbenzene; And mixtures thereof with ethylene. The long-chain macromolecular alpha-olefins are phenyl-terminated Yo polymeric synthetics formed in place during Adal dial polymerization reactions. Under suitable processing conditions these long-chain macromolecular units readily polymerize into a polymeric product together with ethylene and olefin monomers.

1 0. Other short-chain catalysts are used to give small amounts of long-chain branching in the resulting olefinic polymer. The catalysts may also be used in combination with at least one homogeneous or heterogeneous additional polymerization catalyst in the same reactor or in preferably connected reactors. Series or parallel to prepare polymeric mixtures with desirable properties. It shows the desirable properties of © . An example of that process is shown in International Patent 006550/14; equivalent In addition to the US Patent No. 7/90 EVV for US Patent No. ; whose contents are listed here at 1497 + ; Deposited on January 74 18/0858 serial The highly detailed complex compounds have a bond of an offending Ve atom of the pentadinyl group. and when used in a catalytic system of Y=Nitrogen in situ polymerization of olefin with tri(pentafluorophenyl)boron as an activated co-catalyst; Notice an unusual blue color. This could be due to the formation of a moiety cation in which titanium is in; It may exist in a diamagnetic or paramagnetic form, as is (I) the original oxidation Als in the following One 1 /, 0 m Ba:

Se

H; Free 4 pounds

CN

NX

Fs diamagnetic dl 0 with / /

J.O

Ba

Cd

Meh. Fs Fs

AEE NA paramagnetic dl*

011 While reserving our right not to be bound by any particular theory of the mechanism by which this complex compound will be formed; The olefin polymerization catalyst system for the aforementioned olefin polymerization is a co-component 11 (ID). Polymerization can occur when the radical cation is active.

6 For the preferred polymer compositions consisting of olefin polymerization, the subject matter of the invention; which may be produced by the polymerization processes of the subject of the invention using the catalytic systems of the subject of the invention; the long-chain branching is longer than the short-chain branching that results from the insertion of one or more possible conjugate monomers of “-olefin” into the polymer structure; The effect appears due to the presence of a long fork

0 chain in conjugated monomers subject of the invention as improved rheological properties which are inferred by the activation energy of the Uber flux and O/Dy greater than expected from the other structural properties of the formulations. Also the highly preferred polyolefin copolymer compositions of the subject of the present invention have a molecularly reverse engineered shape; That is, there is a maximum value of ve for molecular weight that is found in 0 wt percent of the composition that has the largest conjugate monomer in percent by weight . More preferable also are polyolefin copolymer compositions which are also followed by long-chain branchings along the polymer structure, particularly when they are produced by means of a preservation system or of the present invention having a single complex of methylocene the subject of the present invention in a single reactor in a polymerization process »- olefin with ‎ vo is one or more olefinic conjugate monomers; More specifically when the process is a continuous process. Measurement of the conjugate monomer ratio lie logarithm of molecular weight by CPC/FTIR The conjugate monomer ratio as a function of molecular weight was measured by the value of a FTIR spectrophotometer with C.

Waters 150 6. Gel Permeation Chromatograph (GPC) Yo. And I have explained the setting; Calibration and commissioning of this system

1 (L. J. Rose et al., “Characterisation of Pre-Processing Data”).

Polythylene Copolymers by Coupled GPC/FTIR" in "Characterisations of (Copolymers" Rapra Technology, Shawbury UK, 1995, ISBN 1-85957-048-86). polymer; then using 600/7118 to calculate a criterion called conjugate monomer scattering coefficient; Mw, Mn, Cpf were grown using standard techniques from GPC data.

GPC/FTIR The coefficient of monomer distribution. Conjugate monomer distribution coefficient Cpf is calculated from the GPC/FTIR data. , 0 designates the average ratio of the conjugate monomer present in the higher molecular weight fractions to the average ratio of the conjugate monomer present in the lower molecular weight fractions . The high and low molecular weights were defined by the molecular weight to two molecules of equal weight © and Cpf is calculated from the following equation Sma Emm, pour Cy A wc \o where: © is the ratio of the monthomer molar conjugate and 1717 is the weight ratio as defined by GPC/FTIR for m FTIR data points below mean molecular weight 0 and only those weight ratios ¢ Wi or Wj that accompany ratio values are used Molar molar isomers To calculate Cpf for an available calculation method ¢ the msn must be greater than or equal to Y. Do not enter the FTIR data that corresponds to

Vay in the calculations as a result of the non-oxidation present in the 5,000 molecular weight fractions less than that data. For the polyolefin copolymer compositions the subject of this; and more desirable that 01 is more desirable to be equal to or less than the Cof of the invention; the

CNY; most preferably equal to or greater than 0.05 or greater than gold oo ; It is better for it to be equal to or greater than 1.71, and it is better for it to be equal to or greater than 0.50; Most preferably equal to or greater than 0.48 of A or greater than

ATREF-DV which is herein listed on EVAACAY (in US Patent No. ATREF-DV) 1 “Determination of Short - Chain Branching Distribution of Pavement Reference ¢ Rovey

Ethylene copolymers by Automated Analytical Temperature Rising Elution

Fracationation” (Auto-ATREF), J. of Appl. Pol Set : Applied polymer Symposium is a dual indicator analytical system that ATREF-DV considered 45, 25-37 (1990) as a function of (LLDPE) is capable of experimenting with semi-crystalline polymers such as linear low-density ethylene vo in the crystallization temperature while at the same time estimating the molecular weight of the fragments. And for

Temperature Rising Eultion Ftactionation analogue to ATREF-DV for retail; Fractional distillation is by hyperthermic decantation" that has been published in the publicly available analytical tref literature for the past 10 years. The main difference is that purification is done on a small scale and the fractions are not actually separated. Instead; A typical infrared liquid chromatography mass indicator (ATREF) © Sia-operated single-frequency indicator (IC) is used to quantify the crystal distribution as a function of the decanting temperature and this can then be converted The distribution to any number of alternative domains, for example, a short discharge frequency, the conjugate monomer distribution, or the possible density, and then the solution distribution must then be interpreted according to some structural variables such as the conjugate monomer ratio (Sa Yo m).

Yof often misrepresents LLDPE's for ATREF comparisons although routine use of 0 is made directly in the domain of the decanting temperature; A commercially available viscometer, ATREF-DV, is available for data acquisition with the Vidkotek™ Jie lo infrared mass indicator specially prepared for the analysis of viscosity. ATREF-DV for calculating the viscosity of the red LC thinning agent. These two indicators can be used 0

Mark The average viscous molecular weight of a given fraction can then be estimated using the corresponding original viscosity-fitting constants; And the appropriate coefficients for estimating the concentration of fractions are a typical Houwink ATREF-DV report offi and then; ‎ . Using the given equation Mpf heat of decantation. Then the 0 th ® is calculated. L.A: 0. | Together we do. TREF/DV From the Mpf data, the molecular weight distribution coefficient is calculated by assigning the ratio of the average molecular weight of the fragments with a high percentage of conjugate monomer to the average molecular weight of the fragments with a lower percentage of the conomer. And the high and low conjugate monomer ratio is defined as that which falls below or above 1 degree, respectively ¢, i.e. by dividing the TREF average temperature of the leaching of the special drawing concentration. From the third equation: Mpf hassay fi . into two molecules of equal weight TREF data 5 w;- M;

En

My = ,C A wie M; fim is the viscosity-average molecular weight and 171 is the molar weight ratio as done Mi where for data points « in the fractions below temperature ATREF-DV set by © is Wj is the viscosity molecular weight and is ‎ Mj medium for entertainment. and be

101 For the ATREF-DV data points the gravimetric fraction or gravimetric ratio as determined by the fraction located in the portions below the mean temperature of the clarification . It is only used

SY that accompany the intermediate viscosity molecular weights Wi or Wi those weight ratios ; for an available calculation; and must be “greater than or Mpf than zero to calculate .” is equal to oo and for the polyolefin copolymer formulations in question is equal to or greater than 1.16; Desirably equal to or mPF the 0 of the invention; more desirable equal to or greater than 460; 1.70 is preferred when it is equal to or more than 1.50, and the most preferred is that it is equal to or more than 60; and more. 1.70 preferably also equal to or greater than 01 ½ An experienced person will appreciate that the invention shown here can be made in the absence of any component not specifically shown here. The following examples are prepared to further illustrate the invention and are not specifically meant by By gil. Unless otherwise stated, all parts and proportions are based on weight

Spectra were recorded by Varian XL and 0108 on an HNMR spectrometer (or by 01101MHz (MHz) and the chemical oases were mapped with respect to Yer) and purified TMS was used at 6, 06 for C4HDs left in and 0001 or diethyl ether, toluene and hexane after passing through (THF) tetrahydrofuran catalytically charged double columns of mixed metal oxide backed with activated ammonia and alumina © and all compounds were used. (0- 5© catalyst, available from Enge Hard Crop.) All preparations were made under regular Aldrich Chemical Company grenadine reagents as purchased from n-Bui dry using a nitrogen conjugate. Nitrogen atmosphere, hopping box and high vacuum technologies

Yo example A lithium 1-N-pyrrolidineindenide - N -1 lithium judas pyrrolidineindenide (N=) g of Yo hexane added 00 mL of hexane in

Noland, et al., JOC, 1981, 46, that it is formed by (Ka)N-pyrrolidineindene molar) 70.01(n=BuLi mmol). To this solution was added 4.0 ml of YALA (1940 ©) H with Tripp solid color V4 min. The solution was stirred for 71 minutes by dripping until it was pale yellow. The solid was collected by filtration; washed with hexane; and dried in a vacuum. From the product (70010) to give 7.11 g (the yield of indinyl polypropylene) silane = N - 1- tert-butyl-amino) (dimethyl) = N) preparation (N-t-Butylamino) ( dimethyl) 1-N-pyrrolidineindenyl)silane 01 of 7.11 by THF 001 ml of 001 in the dry box in a round flask stirred 50 ml of a solution and to this solution was added. (Use mVV,Y) CISiMe;NHCMe; Pyrrolidine indenide -17 -1- g (9.7 mmol) of Lithium 7.71 contains 7 droplets. Then the solution was stirred overnight. The solvent was then atomized under reduced pressure; extraction of a hexane precipitate; filtering; And the solvent is dissolved again under ve pressure. gm of output (48 percent yield) 0.111 Low for tender

Poon indenyl polypropylene) =N-1-( preparation of the second lithium (8-butyltriamine) (dimethyl)

Dilithium (N-t-Butylamino) (dimethyl)(1-N-pyrrolidineindenide)silane 2 butyl =N) from (Use mVY) in dry box 0.07 g combined

Ou (Jl pyrrolisine 17 -1(amino)dimethyl) 0 mL 0 with dilithium (N-t-Butylamino)(dimethyl)(1-N-pyrrolidineindenyl)silane) 0.1( n-BuLi mmol) of ¥Y,T) is 16.7 mL of hexane. and to this solution; The solution was stirred overnight. n-BuLi molar) was dripped. ; and upon complete addition to the collection of the precipitate obtained by filtration; and washed with hexane to give 5.97 g (yield .%) of a yellow solid 001 vo

Voy piperolidine-indenyl)=N-1-(butyltri-amino)(dimethyl)(N=) prepare dichloride

I(N-t-Butylamino)(dimethyl)(1-N-pyrrolidineindenylsilane] Titanium

Dichloride

Vo in TIC(THF); Of (Use mm Y1,¥) in the dry box 1.00 g was dissolved and to this solution was added 0.77 g (1.17 mmol) of di. THF mL of © pyrrolidine indinyl (silane) in -37-1(lithium (10-butyltriamino) (dimethyl) solid form with stirring. The solution was then stirred for £0 min. After that, mmol) and stir the solution for 0 £ min. AY) 00012 of V, YY period; ¢ was added under reduced pressure and the precipitate was then extracted with toluene (THF) after which the solution was first filtered; Toluene is denatured under reduced pressure. The precipitate 0 was then titrated with hexane and the solution was cooled to -10°C for 7 hours. The leafy precipitate was collected by filtration and washed with cold hexane. The solid product was dried under vacuum to yield . g (yield 77%) of Yield ©, piperolidine indenyl)silane] titanium =N -1-(ibutyltriamino)(dimethyl) ~N) [ prepared [(N-t-Butylamino)(dimethyl)(1-N- pyrrolidincindenylsilane] Titanium Dimethyl Vo

Dimethyl (17-butyltriamino) dichloride 1,15 In the dry box Pyrrolidine indinyl)silane]titanium (1.0 mmol) was suspended in 00 mL of <7 -1( (dimethyl) molar) by dripping with (7.0 Me Mg Br) ml of 0.00 and to this suspension was added 0.500 min; After completing the addition of 10 minutes, stirring under reduced pressure and extracting the precipitate with hexane; filtering the BO and then the EY body solution was aliquoted; and evaporating the filtrate to dryness under reduced pressure to give weight in percent) of the product. . A (Particular Polymerization Process Alkanes Alkanes ligation of Alkanes solvent 4 0 liter B 1 capacity Parr Yo reactor gm 1117 monomer was charged (Exxon Chemical Inc.) (Available as Isopar-E™ Mixed Type

: 01 as a hydrogen adjusting agent and hydrogen was added. 1-octene octene-1 conjugated from a (differential silo Yo from Lis all molecular weight addition tank by expansion reactor to Cad kPa). YeVe) square inch [Jb Yo] was calcined at 500 C and saturated with ethylene at 060 which had a polymerization heat of psi on the gouge scale (, 4 MPa). The appropriate amount of © toluene of the catalyst and the associated catalyst was pre-mixed as 0 molar solutions in toluene in it ¢ and then the Qt yall solution was transferred, after the pre-mixing period 0 in the dry box, to the catalyst addition tank and entered into the reactor. Polymerization conditions were maintained when needed. The resulting solution, ethylene, was removed by ethylene 10 minutes for a stereoscopic Jy reactor; An antioxidant agent of ga 0 was added

Copia' to the resulting solution. Tragox™ 1010 from Ciba Geigy Corporation was baked for approximately 171 m for the polymers formed in a vacuum oven set at 1 min. The results are listed in Table 0 Table ow | hus | ema | Shera Co ow | Alice (indinyl pyrrolidine) (N=) butyltri-amino) (dimethyl) ([[-1-catalyst] © ve

Catalyst 1-[(N-t-Butylamino)(dimethyl)(1-N-silane)] Titanium ¢pyrrolidineindenyl)silane)] Titanium Dimethyl (dimethyl)(tetramethylcyclopentadienyl) -N ([ -7 Catalyst 2-[(N-t- Jue silane)] Titanium Dimethyl ¢ Butylamino)(dimethyl)(tetramethylcyclopentadienyl)] silane)] Titanium Dimethyl | 0

b Amounts of equal gram molecular weights of the filler and the bound filler were pre-mixed together. c Grams of polymer per gm Ti d Fusion coefficient (dg/min) General Experiments 74-1 BO ; All experiments involving organometallic compounds were performed using dry box techniques. The solvent was 485 (THF) hexane; toluene; ether) by passing through alumina and columns 05.6 were dried under Nak, and vacuum distillation before use. NMR spectra were measured on a 1 FT Varian XL-300MHz instrument; Vo ¢'H MHz; (PC) and 1248.0 1NO and PC{'HINMR) are returned to the maximum values of the purified solvent and are reported in parts per million for tetramethylsilane. All values of [ are reported in Hz. The mass spectrum was obtained. (ED) on Auto Spec QFDP. Endane, MeSiClhsn-Buli MeMglyNa BH, 1112-30, and Bromeld?-Bromoisobutylaryl were purchased from Aldrich Chemical Company. All compounds were used as 0 and then received. Preparation of =F methoxy-111-indine (1984, 106, 6702) (J.AM.

Chem, Soc, © 1973, 27, (Acta Chem Scand. (4027, 1H)-1-7-indenyl)-27 17-dimethylamine (37-1H)-7-indenyl)-27 17-dimethylamine. Pyrrolidine (1973, 27, 4027) (Acta Chem Scand.) and tert-butyl 1H)-7-indioxy)dimethylsilane (Oraganometallics. 1996.15) Y- (2450) by the methods mentioned in the relevant literature. Example 1 ef oY) pe mad 4- tetramethyl BY Ym hydronaphthalene Tetramethyl-2,3-dihydronapthalene 1,1'4,4 Benzene cooled (000 mM (A) and ?-dimethyl (Y— ¥— butanediol (2,3-dimethyl2,3-butanediol ) 8© Yo . gm 741.4 mmol) in an ice bath as YOY, YE can V2 0 ¥0) ALCL ms

0

(Use slowly as a solid for 1 minute under a flow of nitrogen so that it does not increase

the mixture at room temperature. The mixture was kept at room temperature for 10 minutes

minutes and then heated to 0°C for 1 hour. It is important that this interaction is monitored

It is further removed by gas chromatography and terminated when the reaction is complete. and lead

© Changes in the reaction conditions lead to varying reaction omens. After the reaction period, the mixture is filtered over crushed ice carefully to leave behind a thicker yellow oily phase. Done yet

This is to transfer the upper phase of the reaction mixture to the extraction funnel and wash by 1 M

001 H0) XV (ml) and 001 XY) saturated NaHCO; milliliters) ¢ and HCI (XV 001 milliliters). The organic part was then dried over B14850. It is then filtered

0 The mixture and removal of the resulting volatile compounds by separating the desired product as a colorless oil

Raeq ©7.01 (EGP ; yield 87.5 percent).

111 NMr (CDCl3)d1.71 (s, 4 H), 7.1-7.4 (m, 4 H).

*C NMR (CDCl;) d 31.67, 34.19, 35.09, 125.50, 126.45, 144.76.

GC-MS Calculated for C 4H, 188.16, found 188.10. Vo = 11-benzene =A (A 00 0 (Y= preparation 7; 7 0 7-tetrahydro)

©) inden —V — wt. 2,3,5,7-Tetrahydro-2,5,5,8,8-pentamethyl-1H-Benz(f)inden-1-one + Ef stirred 1 1 tetramethyl Y= *- co Og na 0.0 1( 1,1'4,4 Tetramethyl-2,3-dihydronapthalene g 164.7 mL (Js—0 And bromide (Y) bromoisobutyryl (Y) 2-bromoisobutyryl bromide 1 gm 107 mmol) in: 1201© (© lla) liter) at Safram. AIC (44.47 g;

54 mmol) slowly as a solid under a flow of nitrogen for VO min. This mixture was allowed to stir at room temperature overnight. After the interaction period; The mixture was poured onto crushed ice. The organic layer was then separated and Yo washed with 1 M HCl (Yo XV) NaHCO; saturates Yoo XV (mL) and 1001 HO mL). And the organic part was dried above 14850; and his nomination; And then remove the volatiles, which leads to the separation of any dark crystalline precipitate. and perform reset

From diethyl ether (safram) to separate the desired product in the form of a solid lal (75.7 percent of the product yield). (YoY) white crystalline 1.1 NMr (CDCl3)d1.2-1.4 (m, 15 H), 1.71 (s, 4 H), 2.62.70, 21, 3 34 (dd, Jun=17.6 Hz, *Jyy=8.7 Hz, 1H), 7.41 (s, 1H), 7.76 (s , 1H). °

C NMR (CDCl; d 16.50, 31.98, 32.09, 32.14; 34.58, 34.84; 35.25, 42.30, 121.92, 124.18, 133.85, 144.77, 149.94, 152.94, 209.05).

GC-MS Calculated for 0bitter 256.18, found 256.15. Ma - tetrahydro = Aa 1 -; (3-dimethylamino sud) preparation *- Dimethyl 10 ¢ was added by (1) 110 (1) pentmethyl-111- Benz©) indine =A (A© (0 +" mmol) by distillation into a solution of anhydrous dimethylamine Yo, mL hexane 001 mol) in Ale 7960 (aa VY,A ) anhydrous dimethylamine to -40 M. Large blocks of amide Ym with stirring under nitrogen at - tetrahydro-17 0 FY steel begin to form during this process and ve (19.7 mM) is added g) lb.9A) wt -1-pentmethyl-111-benz©) indine = A A 0 © ¥ p00 was then heated to YO and the reaction was allowed to equilibrate to (se The treatment with an equal amount showed the absence of starting material 01 with stirring for a period of time by analysis 11207478. The solution was cooled to 10 m and acetone (approximately 0,000 mg) was added, dried over molecular sieves of type 48, by drip to work on the decomposition of the compound © When titanium amide, the soluble complex consisting of titanium amide, was added to TiO, all the color was changed and acetone was formed. Gila Celite Oxide filtration through

1% as a clear oil which then crystallizes when left (0 a alll mmol) 1 M of hexane in the form of VE-75.5: for overnight stability. melting point Light yellow prismatic Ra (3-(dimethylamino)-5,6,7,8-tetrahydro-2,5,5,8,8-pentamethyl-1H- preparation ° benz(flinde nyl) (lithium, (2).3-(dimethylamino)-5,6,7,8-tetrahydro-2,5,5,8,8-mCr)YO) in pentamethyl-1H-benz hexane) f)inden > (2.11, p 7.46 mmol) pc hy mmol AY 1 molar in hexane 0.10 mL of a solution of 01) n-BuLi Allow this mixture to be stirred overnight and during During this period, a pale yellow precipitate will form. After the reaction period, the desired product was collected by filtration. and washed it with hexane; and dried it under vacuum, which yielded a pale yellow solid isolate for which AY was used without further purification or analysis (0 7.0 g %); The result is 7 ue

HN—t-Bu

01 1-(3-(dimethylamino)-5,6,7,8-tetrahydro-2,5,6,7,8-pentamethyl-1H- ji aa' benz(flin den-1-yl)-N-( 1,1-dimethylethyl)-1,1-dimethylsilanamine, (3).(3- (Dimethylamino)-5,6,7,8-tetrahydro-2,5,5,8,8-pentamethyl-1H-benz( f)inde nyDlithium (1.99, p 6.87 mmol) in THF (30 mL) was added dropwise to a solution

THF in of N-(tert-butyl)-N-(1-chloro-1,1-dimethylsilyl)amine (1.71 p 10.3 mmol) 0 mL). This vinegar was allowed to stir overnight. After the reaction period, the volatile compounds (04) were removed, and the precipitate was extracted and filtered using hexane. The removal of the hexane resulted in the isolation of the desired product in the form of orange oil (7,797 g; 8%). Salt we LiN—t-Ba : 01 preparation of (3-(dimethylamino)-1-((((1,1- pot dimethylethyl)amino)dimethylsilyl)-5,6,7 ,8-tet rahydro-2,5,6,7,8-pentamethyl-1H- benz(f)indenyDlithium, lithium salt, (4).1-(3-(Dimethylamino)-5,6,7,8- tetrahydro- 2,5,6,7,8-pentamethyl-1H-benz(f)in den-1-y1)-N-(1,1-dimethylethyl)-1,1-)dimethylsilanamine 4 g » 7.77 mmol) in hexane (Vo) mL) when vo was added slowly (VY E) nBuli mmol + 1.50 mL of a solution of 011 M in hexane). This mixture was allowed to stir overnight and during that period no precipitate was formed. After that, the solution was placed in the freezer (freezer) 1-0 (m) for a period of time; Days and during that period, pale yellow crystals were formed. The solution was filtered away from Sls

m which was then dried under vacuum and used without further purification or analysis (VY) g; Yield fo %) J 8 ve 1 \ EN a Ta preparation of dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-(3-) dimethylamino)-5,6,7,8-t etrahydro-2,5,5,8,8-pentamethyl-1H-benz(f)inden-1-yl)silanaminato(2-)- © N ) titanium, (5). (3-(Dimethylamino)-1-(((1,1-dimethylethyl)amino)dimethylsilyl)- 5,6,7,8-tet rahydro-2,5,6,7,8-pentamethyl-1H- benz(f)indenyl)lithium, lithium salt 0.1” can 0 mmol) in Ye (THF mmol) to a paste of TiCl3(THF) 1.16 g Yoo A mmol) in THF (04 mL). This mixture was allowed to stir for V0 hours. Then can + (€Y) PHC, 1.08 mM (Use) was added as a solid and the mixture was allowed to stir for an additional hour. After the reaction period, the volatile compounds were removed and the precipitate was extracted and filtered using hexane. The hexane solution was concentrated and placed in the freezer (-10 “C) overnight, and during that period dark purple crystals were formed.Then the solution was clapped and the crystals were dried under 1_ vacuum (77, total throughput). YT in percent).

110 ((3-(dimethylamino)-5,6,7,8-tetrahydro-2,5,5,8,8-pentamethyl-1H- preparation benz(f)ind en-1-y1)-N -(1,1-dimethylethyl)-1,1-dimethyl silanaminato(2-)-

N)dimethyltitanium, (6). Dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-(3- (dimethylamino)-5,6,7,8-t etrahydro-2,5,5,8,8-pentamethyl- 1H-benz(f)inden-1- 0+) mmol) in diethyl ether 0.77 ¢ aa (1,710) yl)silanaminato(2-)-N)tit anium 0 0.1 mmol; 90 milliliters of a solution of 7.71 (Me Mg Br milliliters) when M in diethyl ether is added slowly. After the reaction period, the volatile compounds were removed, and the precipitate was extracted and filtrated using hexane. Hexane removal resulted in the isolation of the desired product in the form of an orange microcrystalline solid (0.66 g; Yield VE in SN CL 1 a b preparation (7) 1-(3,5,6,7-tetrahydro-2-methyl-s-indacen-1-yl)pyrrolidine, 1 ,2,3,5,6,7-Hexahydro-s-indacen-1-one (7.0 g) was treated with 25 g of pyrrolidine 1 °) as in 1 in 100 mL of dry benzene, except that p -toluenesulfonic acid g). The analysis by food chromatography showed that only 75% of the conversion to vo enamine had occurred after 117 hours. While a shift of Av percent occurred after YE hours. Low-boiling ketone distillation gave the amine distillate: ketone ratios (GC) in percent) Yo ive (2.1 g; boiling point = -187 cp VAY at 1 mM) and 88:10 X,Y) g; Boiling point = 147 - 140 C at 1 mm). The viscous precipitate was titrated; dark to give when the solvent is removed (148-197 m at 1 mm). The viscous precipitate was titrated; darkened with hexane to give when the solvent is removed 1500 mg of dark oil selected at 91 in All

of amino acids A and O (als) that were assigned by GC analysis. This material was prepared in relation to the formation of the lithium salt: ox he preparation (8) 1,2,3,7-tetrahydro-6-methyl-5-(1-pyrrolidinyl-s-indacenyl)lithium, 1- (3,5,6,7-Tetrahydro-2-methyl-s-indacen- 1-yl)pyrrolidine (0.64 g, 2.93 mmol) 0 in hexane (mMYo)SA as n-BuLi ) mmol + 0.80 mOa) from a solution of 0.0 M in cyclohexane) slowly. This mixture ol was allowed to stir throughout J and during that section it formed a precipitate. After the reaction period, the desired product was separated in the form of a brown solid after filtration and drying under vacuum and was used without further purification or analysis (0.00 g; Yield Af percent) me HN—t-Bu preparation N-(1,1-dimethylethyl)-1,1-dimethyl-1-(1,5,6,7-tetrahydro-2) -methyl-3- (1-pyr rolidinyl )-s-indacen-1-yl)silanamine, (9). 1,2,3,7-Tetrahydro-6-methyl-5-(1- mmol) in THF (25 mL) was added 2.46 .p 0.55( pyrrolidinyl-s-indacenyl)lithium dropwise to a solution of N-(tert-butyl)-N-(1-chloro-1,1-dimethylsilyl)amine (1.02 00 mmol) 6.13 sold in VO (THF) milliliters). This mixture was allowed to stir overnight. 68

And

After the reaction period, the volatile compounds were AY, and the precipitate was extracted and filtered using hexane. Removal of the hexane separated the desired product in the form of oil

Green (©Af), G; 59 percent). . .

b : 5 Ni is a ° preparation of dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a.8a-.eta.)- 1, 5,6,7-tetrahydro-2-methyl-3-(1-pyrrolidinyl)-s-indacen-1-yl)si lanaminato(2-)- N)titanium, (10). N-(1,1-dimethylethyl)-1,1-dimethyl-1-(1,5,6,7-tetrahydro-2- methyl-3-(1-pyr rolidinyl)-s-indacen-1- yl)silanamine (0.84 g. 2.43 mmol) was stirred in hexane (50 mL) as n-BuLi (4.86 mmol, 2.43 mL of 2.0 M solution in 0 hexane os) when added slowly BuLi -« (87, mmol; 7.47 mL of a solution of 0.0 M in cyclohexane). This mixture was allowed to stir overnight and during that time a small precipitate was formed. The volatile compounds were removed, resulting in the isolation of a dark precipitate. This precipitate was then dissolved in THF (V4 mL) and added dropwise to a paste of TiCI(THF) (1.90 mmol) in THF (04 mL). 1 This mixture was allowed to stir for 1 hour. Then 20012 0.77 CAN 0.797 mmol (mmol) was added as a solid and the mixture was allowed to stir for another y min. After the reaction period, the volatile compounds were treated, and the residue was extracted and filtered using toluene +. Toluene wasolate resulted in a black residue. This residue was then converted into a slurry in hexane and cooled to zero am overnight. The mixture was then filtered, resulting in the isolation of a black, fine-crystalline solid. The step of slurry formation in hexane was then repeated

This pre-filtration boiler was cooled and then the black compound was dried in a 0 YY vacuum (g ¢ yield vy percent). and 0" cl / - . REN a ee Preparation of (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,8a-) .eta.)-1,5,6,7- tetrahy dro-2-methyl-3-(1-pyrrolidinyl)-s-indacen-1-yl)silanaminato(2-)- 0 N)dimethylt itanium, (11). Dichloro(N-(1,1-dimethylethyl )-1,1-dimethyl-1- ((1,2,3,3a,8a-.eta.)-1,5,6 ,7-tetrahydro-2-methyl-3-(1-pyr rolidinyl)-s-indacen-1- mmol) was stirred in diethylether (50 0.76,p yl)silanaminato(2-)-N)titanium (0.37 nL) as MeMgBr (1.53 mmoles, 1.02 mL) 0.17 mL of a solution of “M” in 0 ethyl ether was added slowly. This Jada was allowed to stir after that for an hour. After that, it was isolated This step of slurry formation in hexane and cooling before filtration was repeated and the black compound was dried under vacuum (0 YY; 77 per cent yield).

1-(1H-inden-3-yl)piperidine, (12). According to the general method for _uzasd titanium catalyzed enamine formation of Example 7, dry piperidine (51.4 g, 600 mmol) was treated with TiCl.sub.4 (14.35 g, 75.7 mmol) in 400 mL of CHACI2 is at zero. -1-andanone (cpaVo) 5.6 M mol) was added at this temperature © and the temperature of the reaction mixture was raised to 76 °C. The TH NMR analysis of a treated solution showed a complete transformation of the product. The solvent was oiled by rotary evaporation and the resulting dark oil was aspirated with a residue of 0.110 by 100 mL of hexane. The solution was filtered through a dry silage and evaporated to give a crude product (Yo) (g dark oil). The product was distilled through a 1 diameter Vigreaux column to give a crude product of 1.00 (g; 08.1 m mol) with a yield of VY 0% in the form of light yellow oil (anamin with an area of AA percent by GC analysis (boiling point = 71 °C © 1 mm. No ©

(3-(1-piperidinyl)-1H-indenyD)lithium, (13). 1-(1H-inden-3- jas n- mL of 1 mL of hexane and add YO in yl)piperidine (3.00 g, 15.1 mmol) .fl©, M (1.09 eq.) drip through a syringe for a period of minutes. The elongator was set to 0 and the resulting slurry was allowed to stir. n-BuLi is yellow when the first +0 ml of Ld is added in 50 ml. And after this period; The solid ¢ was filtered and washed by 14 minutes of hexane and left to dry in a vacuum overnight in order to produce the desired anion in the form of a substance

A yellow solid (76, ¥ cu vey m mol) with a yield of 95 percent.

110 1

HN—t-Bu

N-(1,1-dimethylethyl )-1,1-dimethyl-1-(3-(1-piperidinyl)-1H-inden-1-inyl)silanamine, (14). (3-(1-Piperidinyl )-1H-indenyl)lithium (2.96, p 14.4 mmol) “N= (thia-butyl) =N was added dropwise to a solution of THF as £0 mL of ml "01 mol) in VY g; ,01 g; (dimethylsilyl)amine-1 (N=chloro-1)m h. The solution was evaporated in a vacuum Yo for a period £0 min + with continuous stirring for THF of LiCl (ml). And 001 was filtered to give a dark red oil which was dissolved in 1-chloro-hexane (N= (tert-butyl) TN this required and olein the solvent in a vacuum to yield mol) in the form of dark brown oil 1:7 dimethylsilylamine (dimethylsilylamine) 6.0 g; ab | 5M

MTN

Fast paced (1-(((1,1-dimethylethyl)amino)dimethylsilyl)-3-(1-piperidinyl)}- 1H- preparation of indenyl) lithium, lithium salt, (15). In the drybox 4.73 ; (14.4 mmol) of N-(1,1- in dimethylethyl )-1,1-dimethyl-1-(3-(1-piperidinyl)-1H-inden-1-yl )silanamine ) (1m n -BuLi ml (74 m mol) of 17.0 ml of hexane. To this solution, “© yo i” solution was added overnight. The precipitate resulting from BE “n-BuLi was collected by dripping. When the addition was complete ,

11 and dried under reduced pressure to produce (da 01 XY) by filtration and washing with hexane

LAL gm is a yellow solid. The yield was 4 in 0 b a 26 dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-.eta.)-3- (1- preparation of am peridinyl)-1H-inden-1-yl)silanaminato(2-)-N)titanium, (16). (1-(((1,1- 0

Dimethylethyl)amino)dimethylsilyl)-3-(1-piperidinyl)-1H-indenyl) lithium, lithium within 2 minutes of THF ml Yo g; m mol) dissolved in 70” salt and after 1 hour of mixing THF ml of Vo g ¢ 1.18 m mol) in 0.1 TiCI3(THF) g 9.0 m mol) as 70012 Veo added an extra hour. The solvent was then oiled under reduced pressure. The residue was extracted with 0 ml of toluene and filtered through a medium-sized glass medium. The toluene was removed under pressure and the black solid 0. mL-hexane Ye. The residue was crushed (ml) and then dried under low pressure to produce 01 XY crystallized by filtration and washed with hexane.

Ala is a gm produced as a red-brown solid. The yield was 19 in 7 oe 2 nC rN a ae. HC OP \o

Preparation of (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-.eta.)-3-(1- piperidiny 1)-1H -inden-1-yl)silanaminato(2-)-N)dimethyltitanium; 1v). in the dry vessel; Dissolve 1.60 g of dichloro-1 (ON (OV) dimethylethyl)-0; -1 Jb methyl -1( -7- (1 —a7 .af oF XV) -1-biperidinyl) -111-indine -1-yl) © Celan Aminatou (7-)-17 -titanium (©7, m mol) at £0 mL of 320 . To this solution 1.48 mL (7.87 m mol) of 1 (°F) Me Mg was added dropwise and stirred for ½ minutes. And after completing the addition of 1 Me Mg; The solution was stirred for 10 minutes. The 70 was then removed under reduced pressure and the residue was extracted with 1*mL (XY)hexane; The solution was filtered and the filtrate was evaporated to dryness under reduced pressure to give 0.40 g (YY yield in 0%) as a red-orange solid. O 9_

EASY

Ze (N-(1,1-dimethylethyl )-1,1-dimethyl-1-((1,2,3,3a,7a-.eta.)-3-(1-jo asd piperidinyl)-1H-inden -1-yl)sila naminato(2-)-N)((2,3,4.5-.cta.)-2,4-hexadiene)titanium, (18). Dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1- ((1,2,3,3a,7a-.eta.)-3-(1-pi peridinyl)-1H-inden -1-yl)silanaminato(2-)-N)titanium Vo mL of hexane. To this solution ¢ was added 1.78 ml YO m mol) in 111 » g 4.00) ¢ 1.76 ml (0-30 Mg Cl m mol) of 7,;-hexidine immediately followed by adding 11,YY)

Y, 9 m mol (drop by drop). The mixture was shaken for a period of 1 hour and placed in a freezer (Y = 7 m) for three days. Then the solvent was classified and the large black crystals were washed with an amount of 1 ml of cold hexane and dried. in a vacuum to yield 1 mg (<0 percent yield). 2 we ne: a * Preparation of 1-(bromomethyl)-N-(1,1-dimethylethyl )-1,1-dimethylsilanamine, To a stirred solution of 10.00 g (53.32 mmol) of (bromomethyl)chlorodimethylsilane (19) Butylamine in 10 ml Escher. Ve. has precipitated a white solid immediately. The reaction mixture was stirred overnight, filtered through a glass medium, and the additive was removed under reduced pressure to give a colorless liquid. The productivity was AY in percent. ue 8 t-Bu: v4

Preparation of N-(tert-butyl)-N-(1,1-dimethyl-1-((3-tetrahydro-1H-1-pyrrolyl-1H-1- indenyl )methyl)silyl)amine, (20) . To a stirred solution of 3.500 g (15.61 mmol) of compound 19 (last line 4) in 00 mL of THF ,1-dimethylethyl)-1,1-dimethylsilanamine and lithium salt in 0.01 ml of 1117 within 0 minutes. The color of the reaction mixture turned a dark color almost immediately. The reaction mixture was stirred overnight and the solvent was removed under reduced pressure. The remainder was extracted with 0 mL of hexane and filtered. The hexane was removed leaving 4,848 g of red oil. Yield 001 in Ald od ue Nu a * 01 Preparation of N-(1,1-dimethylethyl )-1,1-dimethyl-1-((3-(1-pyrrolidinyl) )-1H-inden-1- yDmethyl)silanamine, dilithium salt with 10 ml hexane, and to this solution 77.7 ml (7.7 mmol) of (pV) n-BuLi was added through A short period of time, an ul addy precipitate appeared by filtration, washed with Av ml hexane, and dried under reduced pressure to yield 0.00 g (yield 001 percent) of Bale ala Vo. Safra & .a > Sa ur a Yu,

\Yo

N-(1,1-dimethylethyl )-1,1-dimethyl-1-(((1,2,3,3a,7a-.eta.)-3-(1- Tahsas_yer in 0. ( ¥ Y ) pyrrolidinyl)-1H-inden-1-yl)me thyl)silanaminato-(2-)-N-)titanium mL of Av in 11 CLs (THF) of (Use pV £,A0 ) dry; 0.00 g gle (YY) and to this solution were suspended; 0.00 g (85,1 M mol) of compound was added. 7

N-(1,1-dimethylethyl)-1,1-dimethyl-1-((3-(1-pyrrolidinyl)-1H-inden-1-yl)me 0

THF ml from ©0 ; Dissolved in thyl)silanamine, dilithium salt was added within 0 minutes. And stir the solution after that for an hour. After this period, 7.18 gm was added per minute. It was then oilized to 1117 under 610 (1.10 m mol) and the solution was stirred for PbCL, from ml of toluene, the solution was filtered, and Te was removed under low pressure. The residue was then extracted with hexane and 50 ml of toluene was collected under reduced pressure. The residue was then pulverized with 0 ml of cold hexane Yo the precipitate by filtering on glass medium; and wash b. It was diluted in a vacuum to give 7.15 g of a black solid. Productivity © percent > 0 Ne =

He” J sr, (N-(1,1-dimethylethyl)-1,1-dimethyl-1-(((1,2,3,3a,7a-.eta.)-3-(1- Preparation) (¥ 9 1117701101 nyl)-1H-inden-1-yl)methyl)silanaminato-(2-)-N-)dimethyl-titanium | 0 (N= )-1(-g dichloro (green - leaf) ) 1.10 cad and in a dry vessel 0 0.440 0 To this solution add BO titanium (©1.7 M mol) in 0 mL of -(“m) dropwise with stirring For 0 minutes, the color of ME Mg 1 has changed from (Usa M YAY) ml, the solution has been stirred for 1 period of Me Mg 1, the solution has changed from black to dark red, and after completing the addition under low pressure, it has been extracted The remaining pixane By © h was then removed to ©, the solution was filtered and the filtrate was evaporated to dryness under reduced pressure to yield (01 Lm XY) g (yield 10%) of a black solid oF.

Prepare 1-(2-methyl-1H-3-indenyl)pyrrolidine, (24). Use 2-Methyl-1-indenone (171° C) in YOu ml of anhydrous benzene. To this solution add 00 ml of pyrrolidinyl. The reaction mixture was refluxed using a Dean-Stark stopcock 0 was infused with YA molecular surfactant products for 10 days. GC analysis showed that the conversion was 71 per cent. The solvent was then separated by distillation and the residue was distilled under reduced pressure (°,/ox (Torr). The first fraction was obtained at Af m while then the desired compound was collected at 177 - 17" m. The yield of yellow liquid was 1.18 gm + EA percent.

0 _: preparation of (YO) » (2-methyl-1-(1-pyrrolidinyl)-1H-indenyl)lithium « and stirred (compound 277). ( 11.771 g 6 41.17 M mol ) in hexane ( You ml ) Lay added aA ) n — Bu Li 2 mol ( £9 ml of KM solution in cyclohexane ( 0. drip) and allowed This mixture was stirred overnight, and a precipitate formed after a period of 1 day, the mixture was filtered, and the desired product was isolated in the form of a yellow solid.

17 dimmer after washing BIXAN and drying in a vacuum and used without other protection or . (machine “AY” 1001% productivity) Analysis 0 ¢

N-(1,1-dimethylethyl)-1,1-dimethyl-1-(2-methyl-3-(1-pyrrolidinyl)-1H- preparation N- THF was added to 100 mL mol) in YO,Y0 g £,YY) inden -l-ysilanamine ©m mol); 1717 ¢ aa¥,0Y) (1,1-dimethylethyl)-1-chloro-1,1-dimethyl -silanamine. within minutes. And the color of the solution turned yellow-orange. THF was dissolved in ml of *0, and the reaction mixture was stirred overnight, then the solvent was oiled under low pressure. Product B was extracted, hexane was removed under low pressure, and the bottle was connected to a tube of 0 ml hexane and filtered 0 5.54, and the yield of the product was 0 Torr) overnight to remove the starting material “01 (high pressure 0). g by a percentage

Lit

Me “Sg (1-(((1,1-dimethylethyl )amino)dimethylsilyl)methyl)-2-methyl-3-(1-) Prepare 0,06 and in a dry container, dissolve (YV) pyrrolidinyl )-1H-indenyDlithiu m, lithium salt

N-(1,1-dimethylethyl)-1,1-dimethyl-1-(2-methyl-3-) — g (16,771 mol) of green 10 d

(1-pyrrolidinyl)-1H-inden -1-yl)silanamine in 100 mL hexane. And to this adapter

11 mL (4.8" M mol) of 0, (n-BuLi M) was added dropwise. When the addition of n was completed

J and collection of precipitate obtained by filtration 0 - e; Stir the solution overnight Bu Li

by 100 ml of hexane and dried under reduced pressure to produce 4.51 g of a yellow solid, with a yield of 8 percent.

wR . Preparation HC Yn, dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-.eta.)-2-methy)

ele gl and in . (YA) » 1-3-(1-pymrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)titanium

The dry suspension of 0.19 m mol) of f(1117) 1101 M was suspended in 00 mL of .THF and to this converter 0 was added 10 0 g (7.1 m mol) (written as compound (YY dissolved in 71 mL of THF through ©

minutes. The solution was then stirred for 00 minutes. After this period, 7.79 g of Pb was added

AVY) CL, m mol) and stir the solution add 00 min. The THF oil is then under pressure

low. The residue was then extracted with Ve ml toluene, the solution was filtered, and the toluene was removed

under moderate pressure. The residue was then pulverized with 0?mL hexane, the precipitate was collected 1 by filtration, washed with 0 lb hexane, and dried in a vacuum to yield 7.78 g of a solid.

black - grey. The productivity was % ©.

Ti on z BN Ny A, Ya.

Preparation of (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-.cta.)-2-methyl-3- (1-p) yrrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium in 00 ml of 0. To this measure add 10 ml (1.98 mmol) of 1 118 146 (m) dropwise, with a decrease of ½ minutes. The color of the solution changed from black to a very dark red. 0 and after adding 1 cliMe Mg to the solution for an hour. The BO was removed under reduced pressure and the residue was extracted with hexane (7077 mL), the solution was filtered, and the filtrate was evaporated to dryness under reduced pressure to yield 1.46 g (yield 1%) of a brown-red viscous residue. 3 No

1-chloro-dimethylsilaneamine -1,0- cyclohexyl ~N- chloro-1 Ve dry preparation in ele gl bottle and in . (¥+) ¢ N-cyclohexyl-1,1-dimethylsilanamine from dichlorodimethylsilane in (Jap) ml (90.94; <1 ml; stirred from (Use M) (Ooo A) 0.1 gm. To this stirred solution, (THF) ml of Ae (about cyclohexylamine lithium) was added slowly as a solid and the stirring continued overnight. It was removed to 2117 in a vacuum, leaving Turbid solution Hexane was added to this mixture and the solids 0 were separated by filtration and washed with hexane The hexane was then removed from the filtrate in a vacuum leaving a product

Clear light green weighs 4.18 g. The productivity percentage was AE percent.

N-cyclohexyl-1,1-dimethyl-1-(3-(1-pyrrolidinyl)-1H-inden-1- aa} yDsilanamine (11, g ¢ YAAY m mol) in THF 101 1H-Y = ¥— indenyl) pyprolidine; lithium salt (¥ 05.14 cpa m mol) dissolved in +0 of THF was added within minutes. The color of the solution changed to a dark red-cherry color immediately. The reaction mixture was stirred overnight, then the solvent was removed under reduced pressure. The product was extracted with 10 mL hexane and filtered. Hexane was removed under reduced pressure. The product was extracted with 610 ml of hexane and filtered. Hexane was removed under reduced pressure and the bottle was connected to a high pressure tube (01 * Torr) for ;; hours to remove the starting material. And 6.77 gm of the product was obtained. The productivity rate was 48 percent. ye 1 prepare __seer (1-((cyclohexylamino)dimethylsilyl)-3-(1-pyrrolidinyl)-1H- iy. (YY) » indenyDlithium, lithium salt dry pot dissolve 5.77 g (71, dammol) of N-cyclohexyl-1,1-dimethyl-1-(3-(1-pyrrolidinyl)-1H-inden-1-yl)silanamine in 100 mL hexane. To this solution was added YE ml (9.79" m) (Use of ne Buli 1 (, m) drip. Upon completion of the addition of n-BuLi; stir the solution overnight. Collect the resulting precipitate by filtration and wash with 001 Hexane was dried and dried under low pressure to produce 11.9 g of yellow substance, and the yield was 94 percent.

1 »

Me we”

LiN—Cy dichloro(N-cyclohexyl-1,1-dimethyl-1-((1,2,3 ,3a,7a-.eta.)-3-(1-) Prepared in the container. (YY) pyrmolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)titanium ml Av V 1101 (THF); To the dry suspension 4.71 g (11.70 mmol) of (((cyclohexylamino)-(1 mmol) of VIVO) 0 g to this solution was added Jy THF pyrrolidinyl -113- indenyl) lithium; Lithium salt dissolved in -1(-3-dimethylsilyl) within minutes. This solution was stirred for 0½ minutes. Following this idea; THF ML from YO

THF and the solution was stirred for + € min. Oil (Use) g of 20012 (748, M Y, 00) 10 ml hexane was added after that under reduced pressure. The residue was then extracted in ml hexane and dried in a vacuum to yield 7.74 g. Fe, the precipitate was collected by filtration and washed with B0 from a dark purple-black solid, yield YY%, Qa 0 preparation (N-cyclohexyl-1,1-dimethyl-1-(( 1,2,3,3a,7a-.eta.)-3-(1-pyrrolidinyl)- of p 0.70 1H-in den-1-yl)silanaminato(2-)-N )dimethyltitanium, ( 34). 1H-0

(V,0Y) inden-1 -yl)silanaminato(2-)-N)titanium m mol) in 56 mL of 2620 and to this solution was added 011 mL (511 m ol) of 1 Me Mg M) J anil with stirring for a period of 0 minutes and the color of the coating changed from black to dark red. After completing the addition of 1 + stirred the solution for an hour. Then oil 0 under low pressure 0 and extract the remaining with hexane ( ) Se 1 01' the solution was filtered and the filtrate a was evaporated dry under reduced pressure to yield 0 1.9 g (yield VA per cent) of a red, crystalline solid CH;

preparation of (7-methoxy-—1H indine) lithium; (70) and Anib *-methoxy = ~1H

0(3-methoxy-1H-indenyl)lithium, (35). 3.Methoxy-1H-indene (4.10 g).

4 m mol) in 001 mM hexane. To this solution was added 1.6 ml of solution

of 0 (n-BuLi m mol) in 10 minutes. And after 1 hour of stirring, the material was collected

pale white sclera; on glass medium and washed with hexane (XY) (© ml)

and dried under reduced pressure to yield 9.77 g to the yield. Yield Ratio AY in

ve cent. N-(1,1-dimethylethyl)-1-(3-methoxy-1H-inden-1 yl)-1,1- dimethylsilanamine ¢ (¥1) was prepared. A solution of =Y was added. Methoxy — 111-Idenyl) Lithium

) yen g “ 14,VYY m mol) in 0?mL of THF within 0 min to 0mL of a solution of 05.77 [aa ¥,YV) (3-methoxy-1H- indenyl)lithium THF m mol). And after completing the addition; The reaction mixture was stirred overnight. The solvent was then oiled under reduced pressure, leaving 0 g of product . The productivity rate is 97 percent. St. Mia 2 A med HN—t-Bu y (1-(((1,1-dimethylethyl)amino)dimethylsilyl)-3-methoxy-1H- Ay. (VV) ¢ indenyl) lithium, lithium salt dry pot; 5.01 g of YA,AY (m mol) was mixed with N N-(1,1-dimethylethyl)-1-(3-methoxy-1H-inden-1-yl)-1,1 - Dimethylsilanamine with A+ ml of hexane. and to this solution; 7.1 ml (0 m mol) (YY,YO) of n-BuLi (1,1) was added by droplet. When the addition of n-BuLi ¢ was completed, the solution was stirred overnight. The resulting precipitate was collected by filtration and washed with #860 mL hexane and dried under reduced pressure to yield 0.0 g of yield. AY Lali percent CH; 0 Og ) Lit Me we" '

LiN—~—t-Bu dichloro(N-(1,1-dimethylethyl)-1-((1,2,3,3a,7a-.eta.)-3-methoxy-1H- Preparation Vo inden- 1-yl)-1,1-dimethylsilanaminato(2-)-N)titanium, (38). (1-(((1,1-

Dimethylethyl)amino)dimethylsilyl)-3-methoxy-1H-indenyl)lithium, lithium salt (0.0 g » 17.46 mm mol) in Yo ml of ThE. To this solution I add,

[ex 4 4( TiCl3(THF); m mol) as a solid and after an hour added X,£Y) PbCl, g + 0.4 m mol) as a solid. After an hour, the reaction mixture was stirred and 70012 (X,£Y) g was added; 4.70 m_mol) as a solid. After an additional hour, the reaction mixture was stirred and the solvent was removed under reduced pressure. The remainder was extracted with 71 ml of toluene and filtered. 0 The toluene was removed under reduced pressure and the remaining pulverized with hexane. The solid was collected by filtration, washed with hexane, and dried under reduced pressure. 7 gm of product was obtained, the productivity rate was 51 percent. The donor of the preparation (N-(1,1-dimethylethyl)-1-((1,2,3,3a,7a-.eta.)-3-methoxy-1H-inden-1- dichloro) N-(1,1-0 p 0.60 ).(39) -dimethylsilanaminato(2-)-N)dimethyltitanium, 71-1 dimethylethyl)-1-((1,2,3,3a,7a-). eta.)-3-methoxy- 1H-inden-1 -yl)-1,1-Y)dimethylsilanaminato(2-)-N)titanium 1.0 m mol) in 50 mL of E20 . To this suspension, 01 ml of (oF)Me Mg I was added dropwise with stirring for 1 min. and at pla) add 1 Me Mg ; The solution was stirred for £4 min. After this section, 1 151060 was removed under reduced pressure, the residue was extracted with hexane, the solution was filtered, and the filtrate was evaporated to dryness under low pressure to yield 1.47 g of the product. Yield percentage AT percent. Moi [WAH vA,

Preparation of “(1H-inden-1-yl)diphenylphosphine (40) . In the dry vessel, lithium inanidide (0 g 10.07 mmol) dissolved in 0 ¾ ml of THF was added over 11 minutes to 0 ml of an ether solution of (AB)phenylchlorophosphine 14.47 (g ¢ 15.07 m (Use (phenylchlorophosphine was distilled prior to application AY) m at a pressure of Torr). After 0 stirring overnight; LICH was separated By filtration to produce a yellow Jaa The solvent was olein in a vacuum leaving a pale white solid This solid was pulverized with 0-hexane The olehexane was olean by slow decanting The solid was dried under pressure

Low to yield 16.47 g of an off-white solid. Yield percentage, AE percent. 01 Preparation of (1-(diphenylphosphino)-1H-indenyl)lithium, (41). (1H-Inden-1-yl)diphenylphosphine )© g; 1.16 M mol) in a mixture of 10 ml of Teg ether and ml of hexane. ne Buli (©7, ml; 8.71 M mol) was added to the mixture within 10 minutes. After stirring all night, the precipitate did not appear. The solvent was oiled under reduced pressure, leaving a waxy yellow residue. This residue was pulverized with 171 ml of hexane for 1 11 minutes. The hexane solution was filtered off and the resulting residue was dried under reduced pressure to yield

8 g of an off-white solid. The productivity rate is 87 percent. 1 Preparation of N-(1,1-dimethylethyl )-1-(3-(diphenylphosphino)-1H-inden-1-yl)-1,1- [ax €,%0) dimethylsilanamine, ( 42). (1-(Diphenylphosphino)-1H-indenyl)lithium ¢

THF mL of a solution of 001 through 388310 to THF mL of 00 M mol) dissolved in 0.07 M01, g YY) NN-(tert-butyl)-N-(1-chloro- 1,1-dimethylsilyl)amine from mol). After stirring all night, it will be a red solution. And remove the solvent in a vacuum

It produces a red oil. The residue was extracted with YO mL hexane and filtered. and remove the hexane

e tarka 17 gm of red colored oil. The productivity rate is 4 percent. Me z wan } preparation of ,1-Dimethylethyl)amino)dimethylsilyl)-3-(diphenylphosphino)- 1-1( 1H-inde nyl)lithium, lithium salt, (43). N-(1,1-Dimethylethyl)-1-(3- 1,YY) (diphenylphosphino)-1H-inden-1-yl)-1 ,1-dimethyl silanamine gterms 0 mol) in hexane (Jo 001) while n-BuLi was added dropwise. This mixture was allowed to stir overnight and a pale white precipitate formed. After the reaction period the mixture was filtered. The desired product was isolated in the form of a pale white solid, which was washed with hexane and dried in Vacuum and used without further purification or analysis (0,4 g; AY percent yield).

(N-(1,1-dimethylethyl)-1-((1 2,3 ,3a,7a-.cta.)-3-(diphenylphosphino )- preparation \o 1H-inden-1-yl)-1 ,1-dimethylsilanaminato(2-)-N)titanium, (44). )1-))))1.1-

¢ Dimethylethyl)amino)dimethylsilyl)-3-(diphenylphosphino)-1H-inde nyl)lithium

Lithium salt To (g TA m mol) in lily (Ja YO) THE to a flake of Ti(CL(THP); (*1.1 g 0 1.80 m mol) in THF (04 ml). This mixture was allowed to stir for an hour. After that, 001 (14, 14 g 67 M) Js was added in the form of a solid and the mixture was allowed to stir for an additional hour. After the reaction period, the volatile substances were oiled and the residue was extracted and purified using toluene. This residue was dissolved in a mixture of hexane "toluene (1/7 h/h)-16 (refined). This step was repeated, resulting in a homogeneous solution which was cooled Gym) overnight, resulting in the precipitation of a purified oil that was Isolated by decantation of the solution and drying in vacuum (YOY) g; yield 84 per cent). 3a,7a-.eta.)-3-(diphenylphosphino)- ( ¢ 0) ¢« 1H-ind en-1-yl)-1,1-dimethylsilanaminato(2-)-N)dimethyltitanium

N-(1,1-dimethylethyl)-1-((1,2,3,3a,7a-.eta.)-3-(diphenylphosphino)-1H-inden-1-yl)-1 was stirred ,1-dimethylsilanaminato(2-)-N)titanium (77 g 173 m mol) ve in SB ethyl ether (00) Lan (Je) add V,£1 Me Mg Br m mol ¢ £4, + ml of a solution of “M in diethyl ether) by drip. This mixture was then allowed to stir for an hour. After the reaction period, the volatile substances were diluted and the resulting residue was extracted using a mixture of hexane / toluene (1/1 h / h). The volatile materials were then filtered in a vacuum, and the residue was re-dissolved and filtered using hexane. Removal of the hexane resulted in the isolation of the remaining product as dark red oil (0 vy YA) g; productivity © percent).

Erd Mian prepared 1H)-1-indiene (Y=yl)pyrrolidine 0 (£7). According to a change of method by Noland et al (Noland, W. E.; Kaneswaran, V. j.Org. Chem. 1981, 46, 1940-1 944) -1-andanone (pa YO) 0.144 mol) was added to 00 mL of polyidene which had been dried 0 over 3A sieves; into a ¥-necked bottle of 500 ml, fitted with a flip-top, a Dean-Stark device and a condenser, which was kept in a dry nitrogen atmosphere. And benzene (Yo) ml of desiccator was added over sieves (4a) and the temperature of the solution was raised to reflux for a period of Vo hour. At the end of this period the analysis of 1117018 of the parent reaction solution showed a ratio of VAY mol per cent of the desired product to 0 Starting material, the total mass of the solvent was deliquescent in a vacuum, and the dark crude product was distilled (Vigeraux column 6) to give a pure growth in the form of oil (eli id YY) g 1.177 mol) with a yield of 71 in cent. The mixture was sensitized from air and water and was transferred to the dry vessel upon distillation. The capillary GC analysis showed the presence of a hexane solution from the distillate with a surface purity of 49 in ll: boiling point = 177 - 175 C_ at 7.0 C; boiling point I - 118 - 17°C at 1 mm; (J

Ya.

(£V) » (1-(1-pyrrolidinyl)-1H-indenyDlithium) 7.8 g (1 VA m mol) of Ja gall (oY) n-BuLi was mixed in the dry vessel. and when jaf add n-buli ; The solution was stirred along the jill, the precipitate was collected by filtration, washed with hexane, and dried under low pressure to yield 1.11 g of the product. Yield 44 in Aldo oO C preparation N-(1,1-dimethylethyl)-1,1-dimethyl-1-(3-(1-pyrrolidinyl)-1H-inden-1- (£A) » yl)sil anamine . and add Js— aa mN (1-(1-pyrrolidinyl)}-1H- YY) indenyl)lithium g ¢ 7761 m mol) in 0 mL of DLATHF 0 1 min to 001 mL THF solution N-(tert-butyl)-N-(1-chloro-1,1- Y,AT) dimethylsilyl)amine g ¢ 17.76 m mol). After completion of the addition, the reaction mixture was stirred overnight. The solvent was then removed under reduced pressure. The remaining Bixan was extracted and the solution was filtered. The solvent was then removed under reduced pressure, leaving ONY g of product. The productivity rate is 906 percent. (J © 3 ve

MN pe \e m

preparation of (1<(((1,1-dimethylethyl )amino)dimethylsilyl )-3-(1-pyrrolidinyl)- 1H-indeny])lithium; lithium salt (£9). In the dry vessel 5.17 g (AVY mol) of NN-(1,1-dimethylethyl)-1,1-dimethyl-1-(3-(1-pyrrolidinyl) was mixed )-1H-inden-1-yl) + with 0 mL hexane and to this VOY mL (7.5*m mol) of n-BuLi (1 M) 0 was added dropwise. And upon completing the addition of 14 n 5 -«. The solution was stirred overnight. The resulting precipitate was collected by filtration, washed with 00 mL hexane, and dried under reduced pressure to yield 5.77 g of product. The productivity rate is 100 percent. L dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a- .eta.)- pian' was commented. (01) « 3 -(1-py rrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)titanjum | 0 ¢ and to this solution. THF ml (71 mmol) in 11.77 « pa, 0) 10) (1-(((1,1-dimethylethyl)amino)dimethylsilyl)-3-(1-pyrrolidinyl)-1H-indenyl ) was added g » 11.77 m mol) in the form of a solid. and after © FY) lithium salt ¢ lithium m mol) in solid form. A mixture of 4.13 0 g (Y, YV) was stirred for 2002 hours. After that, the reaction was added for an additional hour. The solvent was removed under reduced pressure, 0 ml toluene, and filtered. The toluene was removed under pressure 01 and the residue was extracted by . By filtering and washing the reduced al and crushing the remaining with hexane. The article was collected. g of product, 000A hexane, then dried under low pressure. And it was obtained

The productivity rate is 77 percent. aw, om on ed kk

AEA

: wile: sigh

N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-.eta.)-3~(- Preparation of (©Y) pyrrolidiny 1) -1H-inden-1-yl)silanaminato(2-)-N)dimethyltitanium . and dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-.eta.)-3) was suspended from p > 8 46 m mol) at 0100 ( (1-py rrolidinyl)-1H-inden-1-yl)silanaminato(2-)-N)titanium | © From 2020 . And to this absolute was added 1.77 ml of Me Mg I (“m”) dripping with stirring for 10 minutes. When 1 Me Mg has been added, the solution is stirred for £0 min. After this period, oil 0 was induced under reduced pressure, the remaining pixane was extracted, the solution was filtered, and the filtrate was evaporated to dryness under reduced pressure to yield 1.79 g of product 0 . The productivity rate is 87 percent. = ol' (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-.eta.)-3-(1- Preparation) pyrrolidin yl )-1H-inden-1-yl)silanaminato(2-)-N)((2,3,4,5-.eta.)-2,4- hexadiene)titanium « (27). In the dry vessel, 0.460 g of dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-.eta.)-3-() was mixed 1- Chloro(V-14 "Y) with 1/a, g of py mrolidinyl)-1H-inden -yl)silanaminato(2-)-N)titanium

VEY n-BuLi mL of 119 hexadiene suspended in 00 hexane. To this solution was added and then the solution was cooled to a temperature of 0 C (and the solution was kept for two hours 1) the room was filtered and the solvent was removed under low pressure. Dissolve the remainder in as little as possible in PA g of product. Productivity ratio 0.17 m overnight in order for Yom to produce hexane and cool to 100 m m EN

BN text N i | “Za preparation of (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-.eta.)-3-(1-pyrrolidin yl) -1H-inden-1-y1)silanaminato(2-)-N)((2,3,4,5-.eta.)-2,4- pentadiene)titani um » (7*) + dry pot; Dissolve 000 g VV (m mol) of 0 dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-). eta.)-3-(1- py rrolidingl)-1H-inden-1-yl)silanaminato-(2-)-N-)titanium in 10 mL hexane. And to this longing; 4 ml of piperidine (16 mmol) was added immediately; This was followed by the addition of (Ja), Yo by dripping from (oY) n- Bu Mg Cl in hexanes; Y.00 m (Use) and the mixture was refluxed for hours, then the solvent was oiled in the remaining alg space in 16 ml pentane Ve. The solution was aspirated through a glass medium covered with celite and the solvent was oiled in a vacuum. The results were obtained The yield is a dark brown slightly turbid solid 1.497 (g; 5 percent yield).

HC liquefaction: Na / / heat ws Preparation of Dichloro(N-(1,1-dimethylethyl )-1,1-dimethyl-1-((1,2,3,3a,7a) -.eta.)-3- (1-pyrrolidinyl)-1H-inden-1-yl)sil anaminato-(2-)-N-)zirconium + (¢m) NN-(1, 1-Dimethylethyl)-1,1-dimethyl-1-(3-(1-pyrrolidinyl)-1H-inden-1-yl)sil anamine© ¢ di-lithium salt (gm  alarlam mol) slowly as A solid into a slurry of ZrCy (g g + Y,VY mm mol) in toluene (Yeo ml) 0 and this mixture was then allowed to stir overnight and after the reaction period the mixture was filtered and the volatile substances were removed and a tissue was obtained from that Je Desired yield as a golden fine-crystalline solid (1 YYAR) g; Yield 478.9%): recombinant Ba a HC Ci \. preparation (N=(1,1-dimethyl)-1,1-dimethyl-1-((1,2,3) ,3a,7a-.eta.)-3-(1- pyrrolidin yl)-1H-inden-1-yl)silanaminato(2-)-N-)dimethylzirconium « (5 M (0.) Dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-.eta.)-3-(1-py)

<7 a 0.14 pf +,44)rrolidinyl)-1H-inden-1-yl)silanaminato-(2-)-N-)zirconium

mol) in diethyl ether (04 mL) while 1 Me Mg (4.10 M mol + 1.8 mL) was added

of a solution of ¥ M in (AB ethyl ether) slowly. This mixture was then allowed to stir throughout

the night . And after the interaction period; The turpentine material was removed and the residue was extracted and filtered

0 using hexane. The removal of the hexane resulted in the isolation of the desired product in form

red residual (VY) + g ; 749 percent productivity). 5A. Preparation of ~N ¢ N methyl-—1H indine-7-amine » (07). This compound was synthesized

Carlson and Nilsson (Carlson, R., Nilssonn, A.

Acta Chemica changes the general method of

Scan 3, 1984, 38, 49-53) 0. and to a bottle with necks of ¥ 000 ml with a stopper

Upper and buffer Jal and preserved in a nitrogen atmosphere ¢ 1010 ml of hexane was added

Dry. And cool Ad to Yom to spa lagen Yom dimethyl immersion

anhydrous amine 17.3 (g; 1460 mol) in a solvent such that no gas leakage occurred during

Bubble pusher. and to the well-stirred cooled solution 0 was added LAY 21014 g ;

Yo ve m mol) by dripping as the temperature of the vessel is between Voy Yom m (flip warning

Hershberg due to the formation of titanium amide) and the resulting dark brown slurry was stirred for a period of time

0 min was allowed to reach the temperature of safram before adding 1-andanone (37,?

g; 77.7 M mol) instantly combined as a solid. The solution is allowed to

Bring to room temperature and then heated to 10 C for 0 minutes at which point further precipitation

| © from TIO, from the slurry rad the solution is clear and the slurry is filtered through a layer of its thickness; millimeter

of silite dried in an oven under a nitrogen stream and the solvent was removed in a vacuum to yield anamine (¥,A) (g + 77.8 m mol) with a yield of VY% in dark oil form -

Which does not contain a ketone as shown by the analysis by NMR. has been selected

Result at surface purity aA in the machine by GC analysis

a M New 10 Preparation (1-(dimethylamino)-1H-indenyD)lithium » (7*). In the dry vessel © 7.8 g (77.9 mol) of 17; 11-Dimethyl-111-Indene “Yo” amine with 100 mL hexane. To this solution V0 ml (77.5 M (Use of n-30 (1, M)) was added simplified and when the addition of n-BuLi was completed, the solution was stirred overnight. The resulting precipitate was collected by filtration and washed with hexane And dried under low pressure to produce 0.58 g of the product.The yield rate is 91 percent. -1-yl )-N-(1,1-dimethylethyl)-1,1-1 (AQ) dimethylsilanamine . A solution of -1((namethylamino)-~1H indenyl) was added. aa 0 oA) (1-(dimethylamino)-1H-indenyl)lithium a sul ram mol) in 56 mL of THF within a minute to Ar mL of a THF solution of N-(tert-butyl )-N-(1- chloro-1,1-dimethylsilyl)amine | 0) 04,¥ g; — 11.17 M mol). And after completing the addition; The reaction mixture was stirred overnight. The solvent was then removed under reduced pressure. And extract

The remaining hexane was filtered, the solutions were filtered, and the solvent was then removed under reduced pressure LS li 17,000 e yielding 0 yield of 96 percent. BQ a og Me we LIN—t-Bu Preparation (3-(dimethylamino)-1-(((1,1-dimethylethyl)amino)dimethylsilyl)-1H- indenyl)lithium 0 ¢ lithium salt ' (q m) ' and in the dry vessel was mixed ©,ay g of 0.01 m mol) of 1-(3-(dimethylamino)-1H- inden-1-y1)-N-(1,1-dimethylethyl)- 1,1-dimethylsila namine with 0 mL hexane. to this solution. 765.1 mL (£00 m ol) of nBuLi was added and the solution was stirred overnight. The resulting precipitate was collected by filtration, washed with 50 ml of hexane, and dried under reduced pressure to yield 0.60 g of the substance. 0 ratio _productivity 88 percent. Unhappy - HFN Na od Ye, ALI preparation dichloro(1-((1,2,3,32,7a-.eta.)-3-(dimethylamino)-1H- 0 ( 1+) inden-1-yl)-N-(1,1-di methylethyl)-1,1-dimethylsilanaminato(2-)-N)titanium and (3-(Dimethylamino)-1-(((1) ,1-dimethylethyl )amino)dimethylsilyl)-1H- indenyl)lithium \o ¢ lithium salt (0.6 g mmol) in 100 mL of THF . To this solution ¢ was added v) TiCl3(THF); b “g” YAYE m mol) in the form of sale solid.

VEY

m mol) in the form of a solid. The mixture was stirred with 9.0 V (y, 0Y) PBC, and after an hour the reaction was added after that for an additional hour. Oil the solvent under reduced pressure. A ml of toluene was extracted and filtered. The toluene was oleiled under reduced pressure and the remaining Ve was pulverized with the remaining hexane. The solids were collected by filtration, washed with hexane, and then dried under pressure. huh low And then obtaining in gm of product and the productivity rate is 04 percent, demi-sac and other alcohol wh, (1-((1,2,3,3a,7a- eta.)-3-(dimethylamino)- 1H-inden-1-yl)-N~(1,1-dimethylet) Prepare 0,1 g of suspension. (11( + hyl)-1,1-dimethylsilanaminato(2-)-N )dimethyltitanium

Dichloro(1-((1,2,3,3a,7a-.eta.)-3-(dimethylamino)-1H-inden-1-yl)-N- dichloro(1,0Y) (1,1-di methylethyl)-1,1-dimethylsilanaminato(2-)-N)titanjum 0 0 (001 M) ml of 1 148 at 0.17 and to this absolute; BO was added in 460 of Stir the solution for 1 Me Mg 1 min. Upon completion of the addition of 01 dropwise with stirring for 1 ¢ after this period, oil water under reduced pressure and extract the residue with hexane for 0 4 min and evaporate the filtrate to dryness under Low pressure to produce 0.47 g of product.The yield is 860 percent.ve machine == NS sr,

YEA

(1-((1,2,3,3a,7a-.eta.)-3-(dimethylamino)-1H-inden-1-yl)-N-(1,1- sian dimethylet hyl)-1,1 -dimethylsilanaminato(2-)-N)((2,3.4,5-.eta.)-2,4- dichloro(1-) and to 54460 dichlorobodies (17( hexadiene)titanium ((1) ,2,3,3a,7a-.eta.)-3-(dimethylamino)-1H-inden-1-y1)-N-(1,1-di methylethyl)-1,1- mixed/dissolved in 00 mL (Usa M ),V0) dimethylsilanaminato(2-)-N)titanium 0 mL of 1.17 followed by (Use M 1,7(;-X=hexadiene) Hexane” was added and 4 ml of BHO mixture was added and an additional ml of 1 mmol (1 mmol) with (77.7 M B20) in 0.1) BuMgCl was refluxed. The reaction was for 1.0 h, then the reaction mixture was allowed to stir. Overnight, the solvents were perfused under reduced pressure, the residue was extracted with hexane, the solution was filtered, and the filtrate was evaporated to dryness under reduced pressure, and after adding hexane to dissolve the very dark product, the 0 solution was stored in a freezing medium. , g of a crystalline substance The supernatants were concentrated and then cooled in the freezing medium to give an additional product. -diyl)bis(benzene))(1-((1,2,3,32,7a- .eta.)-3-(dimethylamino)-1H-inden-1 -yl)-N-(1, 1-dimethylethyl)-1,1- 10 dimethylsilanaminato(2-)-N)titanium (17) . and in the dry pot; vie g of dichloro(1-((1,2,3,3a,7a-.eta.)-3-(dimethylamino)-1H-inden- 1-yD)-N was mixed -(1,1-di methylethyl)-1,1-dimethylsilanaminato(2-)-N)titanium with oY) g of trans-0-4-biphenylbutadiene and suspended in 1 mL of hexane And to this solution Y. » 717 mL of n-BuLi (1.1 M) was added and the solution was refluxed for

Two hours . The solution was then cooled to room temperature, filtered, and the solvent removed under reduced pressure to give 0,000 g of product. Yield EY percent. The following is the addition of HFN to the preparation of chloro(cyclopentadienyl)(1-((1,2,3,3a,7a-.eta.)-3-(dimethylamino)- 1H-inden -1-y1)-N-(1,1-dimethylethyl)-1,1-dimethylsilanaminato(2-)-N)titanium 0 “¢ (16) and to NY, + g of AB chloro dichloro(1-((1,2,3,3a,7a-.eta.)-3- (dimethylamino)-1H-inden-1-yl)-N-(1,1-di methylethyl)-1 ,1-dimethylsilanaminato(2-)-N)titanium (l-ar m-mol) dissolved in about .feo mL of EHO was slowly added 0.764 m NaCsHs (V0) in Vet (BO m ol The purple reaction mixture was allowed to stir for a day, the solvents were removed under reduced pressure, the residue was extracted with hexane, the solution was filtered, and the filtrate was evaporated to dryness under low pressure. Freezing After removing the supernatants and drying under low pressure, then obtaining the product in the form of crystals in the amount of No 1114, gm, the supernatant was concentrated, then cooled in the freezing medium to give additional product in the form of fine crystals a saar se HC “ea

Yo. cyclopentadienyl(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a- chloro preparation to 0 (£) « .eta.) - 3-(1-pyrrolidinyl)-1H-inden-1-yl )silanaminato(2-)-N)titanium - methylamino)AB) —¥= (maT.7e7 (Ye 1) -1) 71 grams of dichloro

3- adenine (-1-yl) (1) (N= ;-1-dimethylethyl) = AD-1-methylsilane

0 (7-)aminato (N=titanium (77,; m ol) dissolved in about 8-46 mL of

0 was slowly added +,V14 of NaCsHs (1.0 M in (1.0 M mol) (B2O). And he allowed

to the purple reaction mixture by stirring for a day and the solvents were aspirated under pressure

low, extract the residue with hexane, filter the solution, and vacuum the filtrate until

Drying under low pressure. And after adding hexane to dissolve the dark product well;

0 The highly colored purplish-red solution was stored overnight in

freezing method. And after material processing and drying under low pressure ¢ was done

Preparation of cyclopentadienyl-1 (ON) dimethylethyl) = -1-dimethyl-1-

FY) 7 p. -1( -7- (1) —a7 pyrrolidinyl) - 1117- inene -1-yl)silane aminoto

(N- ()-7) titanium 1 (10). To a well-stirred solution of +107 g of ternary)

1 cyclopentadienyl titanium (YTV) m mol) in about *0 mL of ThE slowly added 78 g

of TN((;-1-dimethylethyl)-0; SLB) methyl -1- (-3?-

pyrrolidino-111-indiene-1-yl)silaneamine 7,71 (m mol) as powder

. The yellowish-green reaction mixture (reddish under

incident light) by flipping all night. The solvents were decanted under reduced pressure

0 and the residue was extracted with about Av ml toluene » and the solution was filtered to remove a solid with a solid

A very pale yellow-purple color of the filtrate of a dark olive-green-brown colour

. All parts of the product were dried under low pressure. The dark viscous product was extracted

To dissolve in toluene with hexane and filter and oleate the solvent from the dark brown solution to give

ANY .2 g of product as black powder in appearance (AY %). And he has

-,8 Presence of only broad peaks in the NMR proton region The analysis of a vo proton with M = 1.48 showed a signal at p-EDR ppm. YE

10011 filter B Je dey endl and the faint solid was extracted. 27 (ID) 1,796 g solids were superimposed and filtered and the solvent was dehydrated under reduced pressure to give THF and to a solution of (% LiCsHs; on an AY basis) of a pale pink-purple color ‎; Add THE added in about 10 ml of (Use 7.4 M("LiCsHs" g of 0 M mol). The solution was stirred for about -0 hours. (Bly, 40) of 1.174 gm under low pressure and the remaining two lengths were extracted; filtered and the solvent was removed under low pressure cud to give 0.77 gm of orange powder which turned out to be ferrocene. > Je people Ses

Fo

Ye 1) -1- due AB -1 ;0-dimethylethyl (1-1) -18 chloro preparation Ve (N= (-7) yl)silaneamineto-1-anidine —1H-pyrrolidinyl)-1(-7- (n —a7 . a¥ oF dimethyl-1-1) ~N) g of cyclopentadienyl 074+ into a solution of (V7) titanium.” 1117-pyrrolidinyl)-1(-7-(n —a7 .af »7 «Ye 1((-1- dimethyl-1,0-ethyl) 1-00 titanium (5001) + financier) in about (N= )-7 (YL) Ceylon Aminatou -1- Andin - and it has been transformed (Use m +s) Y) 7001: ; 0448© of NMR of 6 was added in tube of da Vo 30-01 to color the solution immediately to bluish-red. And after about, on the crude reaction mixture. NMR min; Spectra measurements were taken

YY.

0 1011 has 0 AAW - (dimethylamino) - 111- adenine -”-)” —a7 . 7p F Ye 1))-1( preparation of (-Y) dimethylcyanamineto-1 = dimethylethyl)-1(-<7-yl)-1 titanium; (17). and to a solution of (C= phenyl)methyl (N= (dimethylamino-7)((N-

(FY) -1- methyl AB -1 = dimethylethyl (1 - 1) ON) g of FTE 6 (N-(=)yl)silaneamineto-1-pyrrolidinyl) - 1117 -indene -1( -7-) (nq —a7). 01.1176 g of 200 mL of Yo added slowly in about 1797 m (Use) of titanium. 17-dimethylamino(benzyl)lithium (7491© m mol) in powder form (21-7) and the reaction mixture was allowed to stir overnight. The solvents were aliquoted under reduced pressure. The intense dark brown brownish-red solution was extracted and the residue was extracted with hexane. a 0 The highly soluble brown-red solution was filtered from a very dark solid, which is much less soluble in hexane, and each of the product parts was dried under pressure for each of the products (in g) NMR proton. Other iin proton spectra showed after 11 (ID) the presence of broad peaks without characteristics as previously observed for compounds; determined by 1107478 that the original reaction was incomplete PbCl by NMR oxidation of vo samples and filtered and mixed with CeDs and the solid was extracted on the glass medium B. The other resulting fraction The solvent was oiled under reduced pressure and the residue was dissolved in about (-1) to which an additional 01176 g of BO ml of V.O. m mol) as powdered 1,918 methylamino)benzyl)lithium (SUNN total) and after stirring overnight and oligomerization of the solvent under reduced pressure; Subtract the remaining 0

YoY

Bixan and a leachate of some solid matter and a very dark leachate concentrate. The combined solid was placed on the glassy medium in a flask with about 0.075 g of FeCl, and about ¥ ml of THF and left for a Jill. The solvent was oiled under reduced pressure and the residue was extracted with CDs and filtered in an NMR tube. NMR showed the presence of Cp2Fe 0 and a substance that appeared to be a composite of THF from an inorganic substance 1H C¢Dg 72.00 (br 35.1 , 72.0 , 68.2 (br 5). 13C (7 5.06 , (5) 4.01 8) As the filtrate was concentrated, a very dark solid began to separate in the form of crystals, leaving a blood-red, venous-purple solution. The solid material was filtered, washed with hexane, and dried under reduced pressure.The yield was in the form of a reddish-brown dark brown product: 7181g.NMR proton analysis of 0.0749494g of the material in 0606 showed the presence of broad peaks with Undistinguished structure BSR showed a signal at p = 1.58 in agreement with the Til superposition.

Magnetic susceptibility (mg Evan's method), 0V: (Evan's

0 0 Moi A preparation of chloro = a7 . a¥ 7 Ye V)) -1 (f) -7- (dimethylamino) - 111- ve adenine (-1-yl) -1 (N) N=dimethylethyl) = - 1 (7-) dimethylsilaneaminato(N-((?(dimethylamino)phenyl)methyl)titanium; (TA) about 05070 g of PbCI2 was added to a solution of 0. 0774 g of oF Ye (1-1) His.-0-(0=a7(dimethylamino)-111-indene-1-yl(-1;1) N=dimethyl ethyl) = -1-(7-) dimethylsilaneamino (N-((7"-(dimethylamino-?)phenyl)methyl)-0)titanium in 0 about yy to 1 ml of 06M in tube 11408. The reaction mixture was shaken and then left to rest overnight.The NMR spectra showed the presence of two isomers (in a ratio of 1:? approximately) with unique peaks of “HCD”. A small amount Very few compounds of (chloro)(cyclopentainyl) one isomer od phenyl-111-indene-7-amine ¢ (19). In a dry flask ~N- methyl -N preparation ¢ g ) 0) Andatone-1 is equipped with a Dean-Stark diaphragm and a feedback capacitor, then put © . 01 ml) and toluene (Use m VEY 6 m mol) and 37-methylaniline (10.1 g YOY) and a catalyst amount of para-toluene sulfonic acid (+0 g) was added and the mixture was refluxed The reaction and toluene were cooled under low pressure 0 in nitrogen atmosphere for 47 hours before the residue was distilled in vacuum. The high-boiling fraction (0.8 g; °C mm Hg) was collected in the form of amphorae oil, which solidified to substance 1-1001-boil0. A yellow-orange solid when left still. This material was stored in a box. Percent of 77-methylaniline in product 01 in the presence of NMR analysis by other distilled amine did not result in reducing the amount of DU, however; The additional distillation of the unwanted amine in the product. \e

'oo Prepare =F)methylphenylamino)-—1H(indenyl)lithium (V4) and dissolve =Nmethyl ~N—phenyl-111-indiene-3-amine “01. 7 can LA (m mol) in 100 ml of hexane and 011 ml of n-BuLi *,1 M (Eq. 4776) was added dripping through a syringe for 10 minutes and the solution formed a yellow precipitate When n-BuLi was added and the slurry was allowed to stir overnight 0. After this period the solid was filtered and washed with 500 ml hexane and left to dry in a vacuum overnight to give the desired anion in the form of a yellow-orange solid (5 0.87 μm (75.7 m mol) with a yield of 89 percent based on the lithium reagent.

HQ WR 01 preparation of 17-(;-1-dimethylethyl)-0; SE-1-methyl-1-(7-(methylphenylamino)-111-indene-1-yl)slanamine + (.71) solvent =F) (methylphenylamino) -111- indenyl (lithium) (7.01 g; 7.141 mmol) in *0 mL of THF was added dropwise to a solution of tert-butylaminodimethylsilyl chloride (7.17 g) 11.76 m mol) in YO ml of THF for 1 min, with continuous stirring for 1 hr, the solvent evaporated, and the resulting oil was pressurized for 2 hours. Hours and dissolve this oil in 100 ml of hexane and filter out LiCl. Removing the solvent in a vacuum and vacuum volatilization overnight resulted in the formation of the product (6,717 g + 1.7 m mol) in the form of a dark red oil with a yield of 8 percent.

BS Ph'g

Me bis dimethyl ethyl (amino) dimethylsilyl) -?- 1 (1) - 1) was prepared and in the dry container (Y Y) ' (methylphenylamino) - 11- indenyl)lithium' methyl lithium salt (AE-1,0-dimethylethyl)-1(1;=N) mixing 0.47 g (11.7 m mol) of . mL hexane Ae yl)silaneamine with -1- Cpl -~1H (methylphospholamino)- -Y) -1-° in installments. And when (a 1,1) n-BuLi from (Use) 10.8 (0.0 ¥) was added to this solution, and the solution was stirred overnight. The resulting precipitate was collected by filtration, washed with n-BuLi, completing the addition of mL-hexane, and dried under low pressure to give ¥0.£ g of the product. Yield 0 percent. 7 in Ph

Cd "_gp Me

Me between Ve-1-dimethyl-1-dimethylethyl)L-1 (1-N) preparation of dichloroyl)silaneamino-1-(dimethylamino) = 1117 - adenine -- (n —a7 .a¥ 7 Yc) methyl ALD (dimethylethyl)amino (1-1)-1) and (VY)titanium solvent (N - (-7) 11.77 m £, Y0) silyl)-7-(methylphenylamino)-111-indenyl)lithium; Lithium salt 11.77 G 4.7 4( TiCl(THF); 111 mL). To this solution add 0 mol (in 0 m mol) in OAT aa (1.17). 70012 m mol) in the form of a solid. After an hour ¢ yov was added as a solid. The reaction mixture was then stirred for another hour, the toluene was oiled under low pressure and the residue was crushed with hexane. The solid was collected by filtration, washed with hexane, then dried under low pressure ¢ and the Obtaining ov ,/g of product 0, the productivity rate is 954 percent.

Va ( og / we wu b 0 k 1(( -1( -1- dimethyl -1 = dimethylethyl) -1 a 1 ) —N preparation (N- (-Y ) yl)silaneamineto-1-(methylphenylamino)-111-indene-7-(n-87 .a¥-1(1; NN g dichloro 0.460 and tam Suspension (VE) ¢ dimethylaminotitanium on (n 7g- .28 FV Ye )) -1 ) -1- dimethyl-1)-1- dimethylethyl (pA) Titanium (N-)-7(yl)silaneamino-1-(methylphenylamino)-111-indene 0 (0 ¥) Me Mg I mL of +,0Y was added to this suspension. . BO mol) in 560 mL of £0. The solution was stirred for 148 Mg 1 min. And when completing add 01 drip with stirring for a minute. After this period, 1800 was removed under low pressure and the residue was extracted with hexane, which is 1 g of Yo, and the solution was filtered and the filtrate was evaporated to dryness under low pressure to produce the product. The production rate is 976 percent.‎ 1

10 ¢ Methylsilyl)-111-Indene-7-yl)pyrrolidinyl A (chloro-1)-1 preparation Ye, 8 Lithium) 0, g (Ju -1H-pyrrolidinyl) -1) A solution of . (Veo) containing THF ml from a 50 min solution to 1" THF in ml of YO in (Use g 17,776 m mol). After completion of the addition, the reaction mixture was stirred along AY) SiMe;© allylase, the solvent was then removed under reduced pressure, the remaining pixane was extracted, the solution was filtered, and the solvent was then removed under reduced pressure, leaving 7.40 g of the product. MSC ( 0 WIS : MM SrKA -111- (7-(methylphenylamino) -1-dimethyl-1<-phenylmethyl) ) 1-6) preparation and a solution of lithium amide benzene (0.97 g) was added; You min to 10 in THF ml of VO (m mol) in 64 m ATE (chlorodimethylsilyl)-111-indene-“*-yl)pyrrolidine” (7.40 g - (1 mol) After completion of the addition, the reaction mixture was stirred overnight and the solvent was then oiled under reduced pressure. The residue was extracted with hexane and the solution was filtered. The solvent was then oiled under reduced pressure, leaving 7.14 g of the product. Productivity 19 percent.‎ vo

111-04-pyrrolidinyl)-1(-0-((((phenylmethyl)amino)dimethylsilyl)-1(pA preparation) and in the dry vessel; 7.99 g ( VY) ¢ indinyl) lithium; Lithium-111-pyrrolidinyl salt)-1( =)-1-phenylmethyl) —N— dimethyl-1(-1 mol) of mL-hexane and to this solution was added 11.76 ml Av yl) Ceylon Amin with -1- Indin; The solution was stirred throughout the n-BuLi by dripping and upon completion of the addition of (1,1) n-BuLi (m mol) of YA) mL hexane and dried under pressure of 00 overnight. The resulting precipitate was collected by filtering and washing in g of the product; Yield 17 percent. YAY Low; In order to produce 2 “sir a ¥ of ((b -1- (Bue Ji) -<7- methyl A -1) chloro A preparation of titanium; (N -(-7(yl)silaneamineto-1-(pyrrolidinyl)-111-indene-7-(0-27.0-113-pyrrolidinyl)-1(phenylmethyl)amino)dimethyl silyl)-?- (((-1(anip(VA)) and so on. ThE ml of Vo indenyl)lithium salt (7.748 g » 7.97 m mol) in g ¢ 95 m mol) in the form of a solid (Y,490) of the required compound, and (10:) 1117 was added in the form of a solid (Use g; 948, m 1,04) PB and after an hour, mah was added 0. The reaction mixture was then stirred for an additional hour. The solvent was oiled under reduced pressure 1 ml of toluene under reduced pressure and the residue was pulverized with Ve-hexane, the residue was extracted with 0, the solid was collected by filtration, washed with hexane, and then dried under reduced pressure 7.70 g of product was obtained, the productivity rate is 17 percent.

1 "0

(n—a7 . a¥ F Ye 1) -( -1-dimethyl-17-(phenylmeyl)-1) preparation of (YA) moinatite (N) -(-7(yl)silaneamineto-1-(pyrrolidinyl)-111-indene-7- == methyl-7<-(phenylmethyl)JB YY)chloro A g of 1,780 and a suspension of yl) silane -10- adenine —1H - a (pyrrolidinyl) (n —a7 . pg “Ye )) -1 ) °

Grd ml from 0:20. And to this, 50 titanium (14.” M mol) in (N-)-7) aminato min. At 10 minutes by dripping with stirring for a period of (2.0) Me Mg 1, 80 + were added. bored of

EtO min. After this period, “50 minutes of the solution was removed, the solution was stirred for a period of “Me Mg 1 atman”, under low pressure, and the residue was extracted with hexane, and the solution was filtered and the filtrate was evaporated.

At g of product. Productivity ratio 1.77 to dry under reduced pressure to yield 0 percent. : a

LiN—CH—Ph The following are the polymerization data for preservation systems that include metal overlays Led ¥ and a table of this invention is shown.

1 1 table ms | Na Sac 166 M1 [N-(1,1-dimethylethyl)-1,1-dimethyl-1-[(1,2,3,4,5- .gamma.)-2,3,4,5 - 0.895 5 946,000 tetramethyl-2-4-cyclopentadien-1-yl]silanaminato(2-)-N]dimethyl-titanium to > 0,06 | 000 ara | (N«(1,1-dimethylethyl)-1,1-dimethyl-1- ((1,2,3,3a,7a-.gamma.)-3-(1-pyrrolidi nyl)- 0.907 < 0.04 © 2,228,000 1H-inden-t-yl)silanaminato-(2-)-

N-)dimethyltitanium

Y, 8%, 000 «YY in | (14(1,2,3,3a,7a-.gamma.)-3-(dimethylamino)-1H- inden-1-yl)-N-(1,1-dimethyle thyl)-1,1- 0.910 0.22 2,960,000 dimethylsilanaminato(2-)-N) ((2- (dimethylamino-N)phenyl)methyl-C)titanium

AAO « «+ +, YA AAT (N-(1,1-dimethylethyl)-1,1-dimethyl-1- ((1,2,3,3a,7a-.gamma.)-3-methoxy- 0.886 0.38 885,000 1H-inden-1-yl)silanaminato-(2-)-N-)dimethyltitanium

YA Aeon ef > '4.0 (1-((1,2,3,3a,7a-.gamma.)-3-(dimethylamino)-1H-inden-1-y1)-N-(1,1-dimethyle thyl) )-1,1- 0.905 < 0.04 1,808,000 dimethylsilanaminato(2-)-

N)dimethyltitanium 71.8 Law «4:4 (1,1'<(.gamma..sup.4 -1,3-hutadiene-1,4- diyl)bis(benzene))(1-(((1, 2,3,3d,7a-.gamma.)-3- (dimethyl amino)- 0.909 0.07 1,349,000 1H-inden- 1-y1)-N-(1,1-dimethylethyl)-1,1- dimethylsilanaminato(2- )-N) titaniu ed enn eye t «4.4 | (1«((1,2,3.3a,7a-.gamma.)-3-(dimethylamino)-1H- inden-1-y1)-N-(1,1-dimethylethyl)-1,1- 0.908 0.04 5,031,000 dimethylsilanaminato(2-)-N)((2,3,4,5-.gamma.)-2,4-hexadiene)titanium

A- covalent or conserving is B(CeFs) b- g/ Vous c- melting index (g/ 01 min) d- g polymer/g [1 edi ° eGPC analysis that M, - 116 mO/mC - YAY

Determination of the X-ray pentane structure of dichloro(1-15;-1-dimethylethyl)-1)-dimethyl == )) Ye a 4 0— a (n ) = pyridinyl)-111-idein-1-yl)silaneamino (7-)(N-titanium)

data collection

A purple block crystal with dimensions of 0.77 0.71 19 mm was immersed in Paraton, N, Exxon ¢ Cu) and mounted on a thin glass fiber unit. The crystal was transferred to a SMART RLATFORM diffractometer equipped with a monochromatic graphite crystal and two (A 71177 = 4) MoKa radiation sources; and a CCD surface area detector (charged conductive device) which was then kept at a distance of YA, 0 cm from the crystal. And done

ve washed the crystal in a cold nitrogen stream for a period of data collection (-100 m). Three groups, each consisting of 10 frames covering three vertical sectors, were collected using the scanning method © and with an exposure time of ten seconds. Integration of frames followed by determination of reflection coefficients and tuning of minimum angles to form a guiding crystal template and a single row lattice.

Y. The data collection was set up to collect 1781 de gana of frames in four different cycles covering more than one full hemisphere of data. The following table shows a summary of the frame scan variables:

F

x axis | scan capacity | Tires | time. scan | ( ) (#) ! Exposure cycle in seconds

...a

The mm and the last cycle (# ;) indicates a re-scaling of the 0*0 first frame of cycle #1.

This is done to monitor the stability of the crystal and the diffractometer and to correct any diffraction in the crystal. The diffractometer is mounted on a 1.8 mm TOWE device that emits a beam of M-rays A+REX mm. The generator power is set at 04 kV 10 mA. Program 1 was used to set and modify the diffractometer, frame scan measurements, coefficient determination, orientation template calculations, minimum angle adjustments for cell variables, measurements of crystal surfaces, and actual data collection. single crystal data; And reduce it to 0 and prepare it to develop a data collection plan. DATA PROCESSING All 17481 linear crystalline raw frames were read by SAINT software and completed using 30 lateral calculations. The resulting data were annealed to produce 80 reflectances and their estimated standard intensity and neutrality scores. The data were corrected for Lorentz 0 and polarization effects. A total of 16,988 reflections were collected representing an increment level range from 7.7 to 7.49 and including a range of Rsym value equal to ;,; percent; At a minimum of 07

of reflections (+00) and using a correction for crystal decay and was less than 1 in the triangle. The unit cell variables were corrected by the least squares of the Ved (Ved) reflection angles. The following is a statement of the unit cell variables: Mmm 10 (TV) VLA) = B A (£) YLAVIY = b m - AQ) rave aye Cy sal absorption corrections; Using SAD-ABS Sheldrick, GM © (1996) SADABS is a program for using absorption corrections based on effective psi-scan measurements 51, 33-38 Blessing, Blessing R.

H. (1995). Acta Cryst.

A and the absorption equivalent was 1.117 mm 1- and the lower and upper transitions were equal to 4104 , 0 YY respectively. Data processing was carried out using xpert program. The spatial set 0 was determined np2© ;) on the basis of fair absences; The xpert program resulted in the following linear crystalline variables: 0704 unique reflection (Rip = 7.15%) with indices 1-15 162 - 15 13-1- il 1 } The composition was solved by methods Live in SHELXTLS (1995), Sheldrick G.

M. M ‎SHELXTLS.

Crystal-lographic software package.

Siemens Analytics.

Inc. Madison, Wis, USA in which the positions of all atoms other than H were obtained. The structure was also corrected in § “SHELXTL” using the least squares correction of whole cellular material. The non-11 atoms were corrected by the Difference Fourier map and corrected without any hitches. The position of the toluene molecule was determined on the center of reflection occupying the center of the ring. Thus, in Alla, there will be an irregularity or arrangement in the positions of the methyl group that occupy the positions of Ya.

E anal para with a site occupancy factor of 00 per cent for each. In the final round they were 181, 1772 and 8 (quality (I) 67 < 1). 7 of the observed reflections were used with respectively. The utilization was 0.177 percent and the appropriate AVA was 0.04 percent. The residual electron density peaks were (£) 0.0074 = x corrected secondary quenching with the final equal to 0.414 and the Big and Small Fourier-Difference in the presence of a © map.

RI respectively. A correction was made by using the values of 72 instead of the values of 7. The +, YYY familiarity, whose function is not limited, is calculated. In addition, R to get a reference or guide to the value of . 81 Cady The lower functions represent WR2 (Dimethyl (1-OV) = 17) The crystal structure of 1-dichloro compound, and the figure shows 111-pyrrolidinyl (1-) -”- ( dV “a oF 7-01 ((-1- dimethyl-1-N= ethyl) 0 titanium - (N-)7(yl)silane amniato- -1- adenine =

YAY = M,/M, ¢« 117900 - M, GPC showed analysis of dimethylethyl (1-VN) of dichloroX - pentane structure determination by radiology -1-methoxy - 111- adenine -7- (N= 7H.7H F Ye 01 (((-1- dimethyl-1a-0-) titanium (N-)-7(yl) silane aminato 01 Data collection 4 mm (X,Y) Xo, a block-like crystal of a purple color but of dimensions was immersed and mounted on a thin glass fiber unit. The crystal Paraton, N, Exxon was transferred in oil; with a monochromatic graphite crystal and a SMART RLATFORM source to a diffractometer (COD conductor; surface area detector (A 1.7211777 - 3). MoKa radiation ¥-cm from the crystal. The crystal was washed in a stream 0.0 VA charge (which was kept at a distance of m). Three groups were collected, each with a component (001-) cold nitrogen, for the period of data collection, a frame covering three vertical sectors using the scanning method © and with an exposure time of Ye of ten seconds.The integration of the frames, followed by the determination of the reflection coefficients and the adjustment of the angles, resulted in the lowest formation of a crystal guide block and a single-row grid Yo in

The data aggregation was set up to collect a set of 181 frames in four different cycles covering more than one full hemisphere of data. The following table shows a summary of the frame scan variables: x axis, frame capacity, scan time | Scan (#) exposure cycle 0 seconds a and last cycle (# €) refer to sale) Measurement for the first 00 frames of cycle #1 0. This is done to monitor the stability of the crystal and the diffractometer And correct any decrease in the crystal. It includes installing a diffractometer on a 0148 mm caliber device that emits an X-ray beam of 1.8 mm in diameter. The generator power was set at 00 kV 1 mA. The SMART program was used to set and modify the diffraction scale, frame scan measurements, determination of coefficients, steering template calculations, adjustment of minimum angles for cell variables, measurements of crystal surfaces 01, and actual data collection 0. The program was used to develop a data collection plan. Data processing All 181 raw linear crystalline frames were read by SAINT software and completed using 30 lateral calculations. The resulting data were reduced to produce 0 reflectances and their estimated standard neutrality and intensity scores. The data were corrected for Lorentz Vo and polarization effects. A total of YE0£0 reflection representing an increment level range of 7.04 to 7.77 has been aggregated and includes an Rsym value range of 1 percent; at a minimum of 07

And from reflections (000). And using a correction for crystal decay and it was less than 1 in A and the unit cell variables were corrected by the least squares of the angles of determination of 014 reflection. The following is a statement of the unit cell variables: Ar) 7 = a n aera A(£) = 10.17 ( ) Aen = o aera Absorption corrections were made; By using the SAD-ABS program according to the function of Blessing, © and the absorption equivalent was equal to 1.871 mm 1- and the lower and upper transitions were equal to LL and ,547. respectively . Data processing was carried out using xpert program. The stereogroup was determined to be np2 (#0) based on fair absences; the xpert program yielded the following linear crystal variants: 477 unique reflections (Rip = 7.06 percent) with indices = -31 h=30,-15=5.-18=1=19. 00 iy Structure The structure was solved by direct methods in SHELXTLS, in which the positions of all atoms other than H . The syntax has also been corrected in SHELXTL 5; Using least squares correction for whole cellular material. The non-H atoms were corrected by the Difference Fourier | map 0 and corrected without a hitch. And in the final course of correction; Use 7 of the observed reflections with (I) 657 >1 to correct for variable YAY and 101 was WR2 and 5 (Goodness of Fit = 0.00 in All 6.97% (eV, oY) respectively. And using secondary quenching correction with q (ve YY = x). The major and minor residual electron density peaks in the final Fourier e2120 map were equal to VEY and -Yee © , +, respectively. A correction was made using Yu values F2 out of 7 values. R1 is calculated

VTA

Familiar, its function is not limited. In addition, R to get a reference or guide to the value of . RI represents lower functions, not WR; The Jie bi-1 crystal structure of dichloro-17 = (1;1) and shows the form of adenine - TH - methoxy -7- (1) VY oF 7-0) ( (-1-dimethyl-1;0-ethyl) titanium - (N —(Y)yl)silane amniato- -10-0-dimethylethyl)-1 ON) Determination of the pentane structure by 7-rays of dichloro-piperidinyl)-111-indene-1)-Y- (n- a7 .2k Ye)) -y—dimethyl-1)1- . Titanium (N-)-7 (YL) silane aminato -01- Data collection mm YY A block-like crystal with a purple color, but its dimensions 70.74 0.14 Ve ssl, was immersed and mounted on a thin glass fiber unit . Paraton, N, Exxon was transported in oil; Equipped with a monochromatic graphite crystal and a SMART RLATFORM source to a diffractometer (COD device or conductor); and a surface area detector of A 710177 = 1 MoKa (radiation with charge) which was then kept at a distance of 5,171 cm from the crystal. The crystal was washed in a stream of m). Three sets were collected, each with component 0001- (cold TruGNE) for a data collection period of 0 frames covering three vertical sectors using the scanning method © and with an exposure time of 10 out of ten seconds. The integration of the frames followed by the determination of the coefficients resulted in Reflection and angle adjustment The result is a crystal guide template and a grid with a single row of frames in four turns 17781 de gana The data collection was then set up for different collections covering more than one full hemisphere of data. The following table shows a summary ©: For frame scan variables m

Frame capacity axis Scan time 1 Scan (#) exposure cycle . nd secs Ce | Last cycle (# ;) indicates a re-measurement of the first 00 frames of cycle 1. This is to monitor the stability of the crystal and the diffractometer and correct for any pan in the crystal. It includes the installation of a diffractometer on a 1.48 mm tow device that emits a 1.8 mm LOREX beam. The generator power was set at 00 kV 10 mA. Use software 1 to set and modify the diffractometer, frame scan measurements, coefficient determination, orientation template calculations, minimum angle adjustment of cell parameters, crystal surface measurements, and actual data collection. The <cASTO" program was used, shortened and processed, to develop a data collection plan. 01 Data_Processing All 1781 linear crystalline raw frames were read by SAINT software and completed using lateral 3D calculations. The resulting data were reduced to produce hkl reflectances and their estimated standard neutrality and intensities. The data were corrected for Lorentz and polarization effects. A total of 8177 reflections were collected representing a range of 1 level incremented from 0.48 to 1.045 and including a range of Rsym value equal to Y.0 percent; At minimum OY of reflections (+00) and using crystal decay correction it was lower

percent. The unit cell variables were corrected by the least squares of 1 of . Determining angles of 194 reflections (1) rah =a A (1) #dalara =a ) 1( ALYY - M A (1) L¥¥re (V) AY, EAY = A) 0m” =

AT )( ly = v

Blessing, according to the SAD-ABS effect, and absorption corrections ¢ were made using the program, and the lower and upper transitions were equal to 1-1.406 mm, and the absorption equivalent was equal to . respectively, AYA Ae m, and the xpert spatial group was determined, and data processing was performed using the xpert program on the basis of cases of fair absence; The ( ¢ # ) n/p2 program resulted in (1,09 = Rip percent) the following linear crystal variables: 0877 unique reflection -12=h=10,- 12=K. =13,-15=1 - 18.. With the indices of solving and correcting the structure, Ve, in which the positions of SHELXTLS were obtained by direct methods in aS All were solved; Using the SHELXTL 5 correction all atoms other than 11 . The composition was also corrected by means of the H map, and the non-atoms were corrected. ALIS is cellular sald least squares and corrected without any hitches. And in the final course of correction; The Difference Fourier was used to adjust 477 parametres. 181, 1782 and ( ) were 67 > 1 of the observed reflections with 10 4878 respectively. Ve YW percent and .71 percent 7.1 equals AD ( S quality, and the electron density peaks were (v) a 00 YA=x, and using the secondary passivation correction with the final value equal to , 274. And the - Difference Fourier residual major and minor in a map

RI and F are calculated respectively. A correction was made by using the values of 72 instead of the values of 4F

WA

Familiar, its function is not limited. In addition R to get a reference or guide to the value of . 181 represents the lowest functions, not WR2, then calculate the linear absorption equivalent, atomic scattering coefficients, and anticipation corrections

International Tables for X-ray Crystallog- raph International Tables for X-ray from Qayyim

Crystallography (1974). Vol. IV. P. 55 Biringham: Kynoch Press. (Present © distributor, D. Reidel. Dorercht) [N-(1,1-dimethylethyl)-1,1-dimethyl-1- The ¥ figure shows the crystal structure of ((1,2,3,3a,7a- .eta.)-3-(1-piperidiny 1)-1H-inden-1-yl)silanaminato-(2-)-N][(2,3,4,5- ..eta.)-2,4 -hexadiene)] - titanium

All follows the data of the related functions used for syntax selections Lady 1 is the male. equals the number of inversions and © equals the total number of variables n where corrected.

Claims (1)

Claims 1-1 metal complex 00601 according to the formula: “1 F—(% BX m 0 ld which + Hf, Zr, or Ti represents 17 ¢ eX or 1 gal m + when z equals 1 7 represents JO 8 ; And when [ is equal to 7, P INGEST nonhydrogen atoms to 860 non-hydrogen atoms 1 p separately represents a group with 0 hydrocarbyl or hydrocarbyl which represents a substituted hydrocarbyl A or hydrocarbyl - a hydrocarbylamino sid substituent or a hydrocarbyloxy hydrocarbyl optionally substituted with a BR group; and each of the hydrocarbyl hydrocarbylsylyl dds _ 0 or hydrocarbyloxy hydrocarbyloxy saa one or more representing on 1 or the second “hydrocarbylsilylamino” or “hydrocarbylsiloxy 0” or “hydrocarbylsylamine” di(hydrocarbylsilyl)amino 1” or di(hydrocarbyl)amino SL or hydrocarbylamino 0 1 has hydrocarbyl or di(hydrocarbyl) phosphino sis sb (hydrocarbyl) 1 covalently bonded to RP; or optionally two hydrogen atoms other than hydrogen Ye to an bond with each other to form one or more fused ring or ring systems ; 1 Av atom to 1 ; Or a combination of hydrogen separately hydrogen BGR? SRL 28,158 10H or hydrocarbyl, which represents nonhydrogen v4 hydrocarbyl 0 substituted for halo or hydrocarbyl hydrocarbyl substituted for hydrocarbyloxy 1-substituted or hydrocarbyl hydrocarbyl amino hydrocarbylamino 0 substituted or hydrocarbylsilylhydrocarbyl “ve” or optionally two or more than RY, RY RY ,85; RA and 8 covalently bond 1 with each other to form one or more fused rings or ring systems; 1 2 is a JS valence moiety linked to both M© and M by links - from ; where 1" Z contains boron; or a member of group VE of the periodic table of elements ¢ VA also includes nitrogen ¢ phosphorus sulfur sulfur oxygen 4 ‏ XY. is an anionic ligand or dianionic ligand group with up to 1001 atoms except for the type of ligands which are cyclic vy ligand groups linked with Ti electrons not centered; ¥F to be separately at each occurrence of it is a compound of neutral Lewis base having vg up to 10 atoms; Povo is zero 1; or ¥ is less than ? from the original oxidation state (M) YY and when x is an anionic ligand; and when x is a group of vv ligands again dianionic ligand » it is 1 = P ; and YA is zero » 1 or x = Y 1 the a, metal complex of element 1 - where 24 represents 11. 1 ¥ = a, metal complex of element 1 ; Jud RE Cua hydrocarbyl 0 or hydrocarbylsilyl ¢ or hydrocarbyloxy — 0 hydrocarbyl substituent or hydrocarbylamino sisal = hydrocarbyl substituent; hydrocarbyl and 7 represent O or N 1 €—the Ga metal complex of ¥ ¢ Ji RB Cua hydrocarbyl or hydrocarbylsilyl and 7 represents 0 or 17. hand 1 0— Li, metal complex of the element ? ¢ where 23 represents hydrocarbyl ~~ ¥ or hydrocarbylsilyl and 17 represents 1 N +- metal complex (sll) according to element 7 where 1m (RP) group is methoxy methoxy | 1-1 dimethylethyl (fine disilyl)oxy 1,1-dimethylethyl(dimethylsilyljoxy | 0) or dimethylamino sis or A ethyl + amino diethylamino or methylethylamino or methylphenylamino or SD propylamino dipropylamino or dibutylamino + or piperidinyl or morpholinyl or pyrrolidinyl 4 or hexahydrate - -1H oepen-1-yl hexahydro-1H-azepin-1-yl + or 0 hexahydro—(2H) Y=oesineyl-(0:0-1)211:16 or octahydro- 11 1- ionine octahydro-1H-azonin-1-yl -1- or octahydro(2H)1--oicinyl .octahydro-1(2H)-azecinyl 01 1 7#- metal complex according to element 6"; Cua group 1m (RP) stands for ¥ dimethylamino gue or methylphenylamino or piperidingl v or pyrrolidinyl .—A1 Ga, metal complex for element 1; HBL of the format RA Y 2 m 7 patches in which XZ MT ¢ is a cat rang mo; - As previously defined in the aforementioned element 1 4- The metal complex according to element 1; Corresponding to the formula z Squares of cm Which yea for khat p Qat rang m LS is already defined in said element Metal Fail according to metal complex - 01 1 Which Led -2- represents 7-*2- f CR,*SiR*, JCR*; = CR*, JCR*, CR*; J SiR*;SiR*, J CR¥; J stands for +*Byana 2* 0 GeRy* Ar CR*;CR*CR*; § CR%,CR%,SiR*, J SiR,CR*,SiR*, J CR*:SiR*,.CR J; and 0 RY y separately at each occurrence of not a hydrogen or a member selected from "| hydrocarbyloxy, silyl, halogenated alkyl, or halogenated aryl" ; and unions thereof; R*4 having up to 10 non-hydrogen atoms; optionally forming two R*0 groups of non-hydrogen Z)R¥ Cus (not hydrogen ¢ or R* de gana of 7 and group R* Ge 1 7 ring system; ay 7 equals ?; » equals zero; 14 in the original +£ oxidation state; and 3 apart for ay Each occurrence of it is methyl, benzyl, or trimethylsilyl Oise, trimethylsilylmethyl 0, allyl, and pyrrolyl, or two groups X together are 1 1;- butane - 1,4-butane-diyl diyl or 7-butene 1-46-diyl 2-butene-1,4-diyl 0 or SOY oY methyl-7-butene Y = 6 ;- diethyl, 7-methyl-7-butene - and ;- 2,3-dimethyl-2-butene-1,4-diyl, 2-methyl-2-butene-1,4- diyl ~~ 1v or xyyldiyl -11-1 metal complex according to element 7- In which -2- represents 57-*2- and ¥ 7 tmak -ma -PR*- ¢« -NR*- ¢ -S- ; ¢ *2 is CR*, = CR*, J CRY,CR*, J SiR%;SiR*;, Jl CRo* J SiR* or J CR*SiR* 0. For the CR% CR%SiR*; JSiR, CR%SiR*; J or GeR* J CR¥,CR*,CR*; ; And R*y separately at each occurrence is a hydrogen or a selected M-hydrocarbyl member; hydrocarbyloxy or silyl or alkyl halogenated 4 or halogenated aryl » and unions thereof ¢ and the aforementioned R* has 0 to 01 nonhydrogen atoms Optionally two R¥ groups of Z 1 (where R* is non-hydrogen) or an R* group of 7 and R* group of 7 form a yy ring system; PY is 1 , equal to 0; 14 in the original oxidation state + ¢ and 32 for ?- (0)NN-dimethyl)amino 2-(N,N-dimethyl)aminobenzyl, Jiu or 7-(N,N)-dimethyl (0-aminomethyl)phenyl 2-(N,N-dimethylaminomethyl)phenyl or methallyl or trimethylsilylaliyl (Ja) -11-1 metal complex according to the element ¥ where; which led -2- represents 77-*2- f ‎-PR*- ¢« -NR*- ¢ -§- ¢ -O- Tamq 7 ¥ CR,*SiR*, J CR*, = CR*, § CR*CR*, J SiR%;SiR*;, J CR* ar SiRp* as Z* ¢ GeR* § CR%,CR *CR*, J CR*CR*,SiR*, J SiR,CR*;SiR*, of CR%,SIR*CR a 0 ? and 1 R* separately at each occurrence is a hydrogen or a selected M-hydrocarbyl member; hydrocarbyloxy, silyl, halogenated alkyl 4, or halogenated aryl; and unions thereof; And the aforementioned R* yy has up to 10 nonhydrogen atoms “and optionally forms two R* groups YY 1 of 2 (where R* is nonhydrogen atoms; or R* group of Z and R¥ yy group of no ring system; 1 - 7 equals q sia is equal to 1 - the 14 in Alla has the original oxidation +7 and 30 for the 1 Ve; 4- sec = F = Jd butadiene (Y= 1,4-diphenyl-1,3 -butadiene 7-pentadiene oY 1,3-pentadiene 0 4-hexadiene methyl 2,4-hexadiene -11 .1 metal complex according to any of the elements 17-01 where R * The ¥ group represents a single or binary carbon atom bonded to N -14 0 1 metal complex according to element 1, where JAGR is cyclohexyl .isopropyl or cyclohexyl isopropyl : ; which is 1 according to the element metal complex -1#© 1 (t-butylamido)(3-(N-perhydropyridinyl)indene-1 -yl)(dimethylsilane)titanium 7 dichloride; ¥ ‎(t-butylamido)(3-(N-perhydropyridinyl)indene-1 -yl)(dimethylsilane)titanium dimethyl; A (t-butylamido)(2-methyl-3-(N,N-dimethylamino)-4,4,7,7-(tetramethyl)-4,5,6,7 - ° tetrahydroindene-1- yl)(dimethylsilane)titanium dichloride: 1 (t-butylamido)(2-methyl-3-(N,N-dimethylamino)-4,4,7,7-(tetramethyl)-4,5,6,7 - 7 tetrahydroindene-1-yl)(dimethylsilane)titanium dimethyl: A (t-butylamido)(2-methyl-3-(N-pyrrolidinyl)-s-indacen-1 -yl)(dimethylsilane)t itanium q dichloride; 1 (t-butylamido)(2-methyl-3-(N-pyrrolidinyl)-s-indacen-1 -yl)(dimethylsilane)t itanium 11 dimethyl; VY (t-butylamido)(3-(N-perhydropyridinyl)indene-1 -yl)(dimethylsilane)titanium 1,4- VY hexadiene; \¢ (t-butylamido)(3-(N-pyrrolidinyl)indene-1-yl)(dimethylsilane)titanium dichloride; Vo (t-butylamido)(3-(N-pyrrolidinyl)indene-1 -yl)(dimethylsilane)titanium dimethyl; 1" (t-butylamido)(3-(N-pyrrolidinyl)indene-1-yl)(dimethylsilane)titanium dichloride; YYA (t-butylamido)(3-(N-pymrolidinyl)indene-1-yl)(dimethylsilane)titanium dimethyl; VA (t-butylamido)(3-(N-pyrrolidinyl)indene-1-yl)(dimethylsilane)titanium 1,3-pentadiene; 14 (t-butylamido)(3-(N-pyrrolidinyl)indene-1-yl)(dimethylsilane)titanium 2,4-hexadiene; XY. (t-butylamido)(3-(N-pyrrolidinyl)indene-1-yl)(dimethylsilane)zirconium dichloride; 71 (t-butylamido)(3-(N-pyrrolidinyl)indene-1-yl)(dimethylsilane)zirconium dimethyl; YY (t-butylamido)(2-methyl-3-(N-pyrrolidinyl)indene-1-yl)(dimethylsilane)titanium YY dichloride; Y¢ (t-butylamido)(2-methyl-3-(N-pyrrolidinyl)indene-1-yl)(dimethylsilane)titanium Yo dimethyl; A (cyclohexylamido)(3-(N-pyrrolidinyl)indene-1-yl)(dimethylsilane)titanium dichloride; YY (cyclohexylamido)(3-(N-pyrrolidinyl)indene-1-yl)(dimethylsilane)titanium dimethyl; YA (t-butylamido)(3-methoxyindene-1-yl)(dimethylsilane)titanium dichloride; Y4 (t-butylamido)(3-methoxyindene-1-yl)(dimethylsilane)titanium dimethyl; Y. (t-butylamido)(3-(diphenylphosphino)indene-1-yl)(dimethylsilane)titanium dichloride; vy (t-butylamido)(3-(diphenylphosphino)indene-1-yl)(dimethylsilane)titanium dimethyl; vy (t-butylamido)(3-(N,N-dimethylamino)indene-1-yl)(dimethylsilane)titanium ry dichloride; ve (t-butylamido)(3-(N,N-dimethylamino)indene-1-yl)(dimethylsilane)titanium dimethyl; vo (t-butylamido)(3-(N,N-dimethylamino)indene-1-yl)(dimethylsilane)titanium 2,4- 1 hexadiene; vy (t-butylamido)(3-(N,N-dimethylamino)indene-1-yl)(dimethylsilane)titanium 1,4- YA diphenylbutadiene; v4 (.eta..sup.5 -cyclopentadienyl)[(t-butylamido)(3-(N,N-dimethylamino)indene-1- 2 yl)(dimeth ylsilane)]titanium chloride, £3 (-eta..sup 5.-cyclopentadienyl)[(t-butylamido)(3-(N-pyrrolidinyl)indene-1-yl)(dimethyls ~~ ¢¥ ilane)]titanium (III) 3 ).618..5017.5 -cyclopentadienyl)[(t-butylamido)(3-(N-pyrrolidinyl)indene-1 -yl) 2 (dimethyls ilane)]titanium chloride 6 (t-butylamido)(3-(N-pyrrolidinyl) )indene-1-yl)(dimethylsilane)titanium (IIT) 2-(N,N- 7 dimethyl)benzyl B (t-butylamido)(3-(N-phenyl-N-methylamino)indene-1 - yl)(dimethylsilane)titani um 2 dichloride; 4 (t-butylamido)(3-(N-phenyl-N-methylamino)indene-1 -yl)(dimethylsilane)titani um 0.dimethyl; 61 (benzylamido)(3-(N-pyrrolidinyl)indene-1-yl)(dimethylsilane)titanium dichloride; or oY (benzylamido)(3-(N-pyrrolidinyl)indene-1 -yl)(dimethylsilane)titanium dimethyl. oy prepared from the components of the olefin polymerization system catalyst catalyst system-11-1: including catalyst stirrer y ¥ ( ) a catalyst fraction comprising a metal compound according to element 1 ; And ¢ (b) A catalyst fraction incorporating an activated co-catalyst where the molecular ratio is between (a) oo and (b) 1:00001 to Adee -11 1 An olefins polymerization process involving contact with one or more alpha " - 8 Cp olefins under polymerization conditions with a La, catalyst oY catalyst system of element 11 .