CN1231668A - 2-heteroatom substituted cyclopentadienyl-containing metal complexes and olefin polymerization process - Google Patents

Abstract

The present invention relates to heteroatom-substituted cyclopentadienyl-containing ligands, metal complexes containing these ligands, catalyst systems prepared from catalyst components comprising these metal complexes. The metal complex contains a heteroatom- _Cp bond at the 2-position of _Cp or a heteroatom- _Cp bond on the ring. In a preferred metal complex, the ligand is a 2-heteroatom substituted indenyl. The catalyst system of the present invention for olefin polymerization can be used at high temperatures, is highly active, and can produce high molecular weight polymers.

Description

Cyclopentadienyl metal complexes containing 2-heteroatom substitution and olefin polymerization method

Cross References to Related Applications

This application claims priority from US provisional application 60/034,819 (filed December 19, 1996) and 60/023,768 (filed August 8, 1996).

The technical field of the present invention

The present invention relates to metal complexes, ligands for the preparation of these metal complexes and olefin polymerization catalysts derived therefrom which are particularly suitable for use in processes for preparing polymers by polymerizing alpha-olefins and mixtures of alpha-olefins.

Background technique

Confined geometry metal complexes and methods for their preparation are disclosed in US Application Serial No. 545,403 (EP-A-416,815), filed July 3, 1990, and US Application Serial No. 547,718, filed July 3, 1990 (EP-A-416,815). A-468,651), US Application Serial No. 702,475 filed May 20, 1991 (EP-A-514,828), US Application Serial No. 876,268 filed May 1, 1992 (EP-A-520,732) and 1993 US application serial number 8,003 (WO 93/19104) filed on March 21, and US-A-5,055,438, US-A-5,057,475, US-A-5,096,867, US-A-5,064,802, US-A-5,132,380 and WO95/ 00526 in. All of the above patents or corresponding US patent applications are hereby incorporated by reference.

US 5,350,817 and 5,304,614 disclose zirconium complexes with bridged metallocene ligands for polymerizing propylene in which two indenyl groups are covalently bonded together via a carbon or silicon containing bridge.

EP-A-577,581 discloses asymmetric bis _-Cp metallocenes containing fluorene ligands with heteroatom substituents.

E.Barsties, S.Schaible, M.-H.Prosenc, U.Rief, W.Roll, O.Weyland, B.Dorerer, H.-H.Brintzinger Journal of Organometallic Chemistry (J.OrganometallicChem.), 1996, 520, 63-68; and H.Plenio, D.Birth Journal of Organometallic Chemistry, 1996, 519, 269-272 disclose such systems for the formation of isotactic polypropylene and polyethylene in which the ring of indene Pentadienyl is substituted with dimethylamino in non-bridged and silicon-bridged bis-indenyl.

R.Leino, HJ.K.Luttikhedde, P.Lehmus, C.-E.Wilen, R.Sjoholm, A.Lehtonen, J.Seppala, JHNasman Macromolecules, 1997,30,3477-3488 published in _C2 -bridged bis-indenyl metallocenes with oxygen in the 2-position of the indenyl group, published by IMLee, WJGauthier, JM Ball, B. Iyengar, S. Collins Organometallics, 1992, 11, 2115-2122 C ₂ -bridged bis-indenyl metallocenes with oxygen in the 5,6-position of the indenyl group, N. Piccolravazzi, P. Pino, G. Consiglio, A. Sironi, M. Moret Organometallic Chemistry, 1990, 9 , 3098-3105 disclose non-bridged bis-indenyl metallocenes having oxygen at the 4 and 7 positions of the indenyl group.

It has long been believed that heteroatom substitution at any position in the indenyl system of metallocene complexes, as opposed to carbon or H substitution, reduces the catalyst activity when used as an olefin polymerization catalyst, in other words, for the efficiency of an α-olefin polymerization catalyst. Lower, the produced polymer has lower molecular weight and lower isotacticity. The reduced activity of this broad class of catalysts is thought to be due to the interaction of the lone pair of heteroatom electrons with the Lewis acid cocatalyst polymerization activator, leading to the formation of a _Cp ring that is more electron deactivated (while the _Cp is more sterically hindered). )the result of. See P. Foster; MD Rausch; JCW Chien. Journal of Organometallic Chemistry, 1996, 519, 269-272.

Random heteroatom substitution in mono- _Cp metallocenes is disclosed in EP-A-416,815, WO95/07942, WO96/13529, U.S. 5,096,867 and 5,621,126 and related applications.

Hitherto it has been considered that heteroatom substitution in metallocene complexes used as polymerization catalysts is disadvantageous because the lone pair of electrons of the heteroatom interacts with transition metal atoms of the same or different metallocene molecules, or with other components of the catalyst system. due to unwanted interactions of components.

Many improvements have been made to various metallocene complexes useful as olefin polymerization catalysts. However, there are still issues of catalyst efficiency and deactivation under high temperature polymerization conditions. It would be desirable to be able to produce higher molecular weight polyolefins. It would also be advantageous to be able to enhance other physical properties of the polymer produced by varying the substitution profile on the cyclopentadienyl group of the metallocene complex used in the olefin polymerization catalyst system. A new class of metallocene complexes for use in olefin polymerization catalyst systems may provide a solution to the above-mentioned problems and provide advantages over other solutions.

SUMMARY OF THE INVENTION

According to the present invention, there is provided a metallocene complex conforming to the following general formula:

Wherein M is a metal selected from Groups 3 to 13 of the periodic table, lanthanides or actinides, and its apparent oxidation state is +2, +3 or +4, and the metal is combined with a cyclopentadienyl (Cp ) π-bonding, the cyclopentadienyl group is a cyclic delocalized π-bonding ligand group with 5 substituents ( ^RA ) _j -T, ^RB , ^RC , ^RD and Z , wherein j is 0, 1 or 2; R ^A , R ^B , R ^C , R ^D are R groups; where

T is a heteroatom covalently bonded to Cp ring, when j is 1 or 2, and ^RA , when j is 0, T is F, Cl, Br or I; when j is 1, T is O or S, or N or P and there is a double bond between R ^A and T; when j is 2, T is N or P; wherein

^RA is independently hydrogen or a group having 1 to 80 non-hydrogen atoms, said group being hydrocarbyl, hydrocarbylsilyl, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl Hydrocarbyl, hydrocarbylamino, di(hydrocarbyl)amino, hydrocarbyloxy, each ^R optionally substituted by one or more substituents independently of each other being hydrocarbyloxy having 1 to 20 non-hydrogen atoms , Hydrocarbylsiloxyl, Hydrocarbylsilylamino, Di(hydrocarbylsilyl)amino, Hydrocarbylamino, Di(hydrocarbyl)amino, Di(hydrocarbyl)phosphino, Hydrocarbyl sulfide, Hydrocarbyl, Halogen-substituted hydrocarbyl, Hydrocarbyloxy-substituted hydrocarbyl , hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl, or non-interacting groups with 1 to 20 non-hydrogen atoms; each of R ^B , R ^C and R ^D is hydrogen, or has 1 to 80 non-hydrogen atoms A group of a hydrogen atom, said group being a hydrocarbyl, a halogen-substituted hydrocarbyl, a hydrocarbyloxy-substituted hydrocarbyl, a hydrocarbylamino-substituted hydrocarbyl, a hydrocarbylsilyl, a hydrocarbylsilylhydrocarbyl, each of R ^B , R ^C and R ^D optionally being One or more substituents are substituted, and the substituents are independently alkoxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di(hydrocarbylsilyl)amino, hydrocarbylamino, Di(hydrocarbyl)amino, di(hydrocarbyl)phosphino, hydrocarbyl sulfide, hydrocarbyl, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl, or having 1 to 20 non- no interacting groups of hydrogen atoms; or optionally two or more of ^RA , ^RB , ^RC , and ^RD are covalently bonded to each other to form 1 to 80 non-hydrogen atoms for each R group 1 or more fused rings or ring systems, which are unsubstituted or substituted with one or more substituents independently of each other having 1 to 20 Hydrocarbyloxy, hydrocarbylsilyloxy, hydrocarbylsilylamino, di(hydrocarbylsilyl)amino, hydrocarbylamino, di(hydrocarbyl)amino, di(hydrocarbyl)phosphino, hydrocarbyl sulfide, hydrocarbyl, halogen substitution of non-hydrogen atoms hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl, or non-interacting groups having 1 to 20 non-hydrogen atoms;

Z is a divalent moiety bonded to Cp and M through a σ bond, wherein Z includes boron, or an element of group 14 of the periodic table, and also includes nitrogen, phosphorus, sulfur or oxygen;

X is an anionic or dianionic ligand group having up to 60 atoms, excluding cyclic delocalized π-bonding ligand group-like ligands;

X' are independently of each other neutral Lewis base coordination compounds having up to 20 atoms;

p is 0, 1 or 2, and p is 2 less than the apparent oxidation state of M when X is an anionic ligand; p is 1 when X is a dianionic ligand; and

q is 0, 1 or 2.

The above-mentioned complexes may optionally be in the form of pure isolated crystals, or in the form of mixtures with other complexes, or optionally in the form of solvated adducts in solvents (especially organic liquids), as well as dimers or chelates thereof. In the form of complex derivatives, the chelating agent is an organic substance, preferably a neutral Lewis base, especially a trihydrocarbylamine, a trihydrocarbylphosphine or a halogenated derivative thereof.

The present invention also provides a catalyst system for the polymerization of olefins prepared from catalyst system components comprising:

(A) a catalyst component comprising a metal complex of the aforementioned complex; and

(B) a cocatalyst component comprising an activated cocatalyst, wherein the molar ratio of (A) to (B) is 1:10,000 to 100:1; or (A) is activated by an activation process.

Another embodiment of the present invention is a catalyst system for the polymerization of olefins prepared from catalyst system components comprising:

(A) a catalyst component comprising a metal complex of the aforementioned complex; and

(B) a cocatalyst component comprising an activated cocatalyst, wherein the molar ratio of (A) to (B) is 1:10,000 to 100:1

Wherein the metal complexes are in the form of cationic groups.

The present invention further provides a process for the polymerization of olefins, comprising contacting one or more _C2-20 α-olefins with one of the above catalyst systems under polymerization conditions.

A preferred process of the present invention is a high temperature solution polymerization process for the polymerization of olefins comprising contacting one or more _C2-20 alpha-olefins with one of the catalyst systems described above at a temperature of from about 100°C to about 250°C under polymerization conditions .

Polyolefin products produced by the above methods are also within the scope of this invention. Preferred products have long chain branches and inverted molecular structures.

The present invention also provides a cyclopentadienyl-containing ligand of one of the above metal complexes, wherein the ligand is in the following form:

(A) a free base with 2 protons capable of removal;

(B) dilithium salt;

(C) magnesium salt; or

(D) Mono- or disilylated dianions.

Use of one of these ligands for the synthesis of metal complexes according to the invention, or for the synthesis of metal complexes comprising a metal from groups 3 to 13, lanthanides or actinides of the periodic table and 1 to 4 ligands The use of substances is also within the scope of this aspect of the invention.

The catalysts and processes of the present invention achieve high production efficiencies of high molecular weight olefin polymers over a wide range of polymerization conditions, especially high temperatures. They are especially suitable for solution or bulk polymerization of ethylene/propylene (EP polymers), ethylene/octene (EO polymers), ethylene/styrene (ES polymers), propylene and ethylene/propylene/diene (EPDM polymers) , wherein the diene is ethylidene norbornene, 1,4-hexadiene, or a similar non-conjugated diene. The use of high temperatures significantly increases the productivity of these processes because polymer solubility increases at high temperatures, allowing high conversions (higher polymer product concentrations) to be employed without exceeding the solution viscosity limits of the polymerization equipment, while Reduce the energy required to devolatilize the reaction product.

The catalysts of the present invention may also be supported on a support material and used in slurry or gas phase olefin polymerization processes. The catalyst can be prepolymerized in situ with one or more olefin monomers in the polymerization reactor, or the catalyst can be prepolymerized in a separate step prior to the main polymerization and the prepolymerized catalyst intermediate can then be recovered.

So far it has been thought that direct substitution of heteroatoms on the cyclopentadienyl (C _p ) group, which is the cyclic delocalized π-bonded ligand group of metal complexes, is critical for the complex's role in olefin polymerization catalyst systems. There is no beneficial effect in application. However, it has now been found that the preferred metallocene complexes of the invention with direct substitution of heteroatoms on a single π-bonded _Cp group have unexpected properties as olefin catalysts, allowing the production of High molecular weight polymers with desired properties. Metallocene complexes with the desired substituted heteroatom in the 2-position are particularly preferred.

Brief description of the drawings

Figure 1 gives dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-dimethyl Crystal structure of amino-1H-inden-1-yl)-silanaminato-(2-)-N-)-titanium.

Figure 2 gives ([N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-ethoxy Crystal structure of -1H-inden-1-yl)-silaneammine-(2-)-N-)dimethyltitanium. A detailed description

All references herein to the Periodic Table of the Elements are to the Periodic Table of the Elements published and copyrighted by CRC Press Inc. 1989. All references to groups shall be to the groups reported in the Periodic Table of the Elements using the IUPAC system for group numbering.

The olefins used here are _C2-20 aliphatic or aromatic compounds containing ethylenically unsaturated bonds, and cyclic compounds such as cyclobutene, cyclopentene and norbornene, including C _1-20 hydrocarbyl substituted norbornene. Also included are mixtures of these olefins and mixtures of these olefins with _C4-40 diene compounds. Examples of C _4-40 diene compounds include ethylidene norbornene, 1,4-hexadiene, norbornadiene, and the like. The catalysts and processes herein are particularly useful for the preparation of ethylene/1-butene, ethylene/1-hexene, ethylene/styrene, ethylene/propylene, ethylene/1-pentene, ethylene/4-methyl-1-pentene And ethylene/1-octene copolymers, and terpolymers of ethylene, propylene and non-conjugated dienes, such as EPDM terpolymers.

Preferred X' groups are: carbon monoxide; phosphines, especially trimethylphosphine, triethylphosphine, triphenylphosphine and bis(1,2-dimethylphosphino)ethane; P(OR ⁱ ) ₃ , wherein R ⁱ is a hydrocarbon group, a silyl group or a combination thereof; an ether, especially tetrahydrofuran; an amine, especially pyridine, bipyridine, tetramethylethylenediamine (TMEDA) and triethylamine; an alkene; and having 4 to 40 Conjugated diolefins with carbon atoms. Complexes containing the latter X' group include those in which the metal is in the +2 apparent oxidation state.

Preferred coordination complexes of the present invention are complexes meeting the general formula:

Wherein R ^W , R ^X , ^RY and R ^Z are R groups, and each group is independently hydrogen, or a hydrocarbon group having 1 to 80 non-hydrogen atoms, a halogen-substituted hydrocarbon group, an alkoxy-substituted hydrocarbon group, a hydrocarbon amino-substituted hydrocarbyl, hydrocarbylsilyl, hydrocarbylsilylhydrocarbyl, each of ^Rw , ^Rx , ^RY , and ^RZ is optionally substituted with one or more substituents each independently having 1 to 20 non-hydrogen Atomic hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di(hydrocarbylsilyl)amino, hydrocarbylamino, di(hydrocarbyl)amino, di(hydrocarbyl)phosphino, hydrocarbyl sulfide, hydrocarbyl, halogen substituted hydrocarbyl, Hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl, or non-interfering groups having 1 to 20 carbon atoms; or R ^W , R ^X , ^RY , R ^Z , R ^A and Two or more of R ^B are optionally covalently bonded to each other to form one or more fused rings or ring systems having 1 to 80 non-hydrogen atoms per R group, the one or more fused rings Or the ring system is unsubstituted or replaced by one or more hydrocarbyloxy, hydrocarbylsilyloxy, hydrocarbylsilylamino, di(hydrocarbylsilyl)amino, hydrocarbylamino, di( Hydrocarbyl)amino, di(hydrocarbyl)phosphino, hydrocarbyl sulfide, hydrocarbyl, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl, or a group having 1 to 20 carbon atoms Non-interfering group substitution.

Preferred ^RA groups are those wherein ^RA is hydrocarbyl, hydrocarbylsilyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl and T is O or N, more preferably wherein ^RA is hydrocarbyl or hydrocarbylsilane and T is O or N, even more preferred are those wherein ^RA is hydrocarbyl or hydrocarbylsilyl and T is N.

Preferred heteroatom-containing substituents at the 2-position of Cp are wherein ( ^RA ) _j -T is dimethylamino, diethylamino, methylethylamino, methylphenylamino, dipropylamino , Dibutylamino, piperidinyl, morpholinyl, pyrrolidinyl, hexahydro-1H-azepin-1-yl, hexahydro-1(2H)-azocinyl, octahydro-1H-even Nitrin-1-yl, octahydro-1(2H)-azocinyl, methoxy, ethoxy, propoxy, methylethoxy, 1,1-dimethylethoxy, tri Those groups of methylsilyloxy or 1,1-dimethylethyl(dimethylsilyl)oxy. More preferred are those wherein ( ^RA ) _j -T groups are methoxy, ethoxy, propoxy, methylethoxy, 1,1-dimethylethoxy, trimethylsilyloxy group or 1,1-dimethylethyl(dimethylsilyl)oxy group.

In another embodiment of the invention, the ligand or metal complex has one or more fused rings or ring systems in addition to _Cp or indenyl, wherein one or more fused rings or ring systems contain one or more N, O, S or P ring heteroatoms. Preferred ring heteroatoms are N or O, with N being more preferred.

其中的各符号如前所述。Other very preferred complexes correspond to the general formula: Wherein each symbol is as defined above, or the more preferred complex conforms to the following general formula:

The symbols are as described above.

Very preferred are metal complexes and their heteroatom-containing ligands wherein Z is -Z ^* -Y-, Z ^* is bonded to _Cp , Y is bonded to M, and

Y is -O-, -S-, -NR ^* -, -PR ^* -;

Z ^* for SiR ^* ₂ , CR ^* ₂ , SiR ^* ₂ , SiR ^* ₂ , CR ^* ₂ , CR ^* ₂ , CR ^* =CR ^* , CR*2, SiR ^* ₂ , CR ^* ₂ , SiR ^* ₂ ^, CR ^* _{2 ,} SiR ^* ₂ CR ^* ₂ SiR ^* ₂ , CR ^* ₂ CR ^* ₂ SiR ^* ₂ , CR ^* ₂ CR ^* ₂ CR ^* ₂ , or GeR ^* ₂ ; and

R ^* are independently hydrogen, or groups selected from hydrocarbyl, hydrocarbyloxy, silyl, haloalkyl, haloaryl, and combinations thereof, said R ^* having up to 20 non-hydrogen atoms, and optionally Two R ^* from Z (when R ^* is other than hydrogen)/or one R ^* from Z and one R ^* group from Y form a ring system;

where p is 2, q is 0, M is in the apparent oxidation state of +4, and X are independently methyl, benzyl, trimethylsilylmethyl, allyl, pyrrolyl, or two X The groups together are 1,4-butanediyl, 2-butene-1,4-diyl, 2,3-dimethyl-2-butene-1,4-diyl, 2-methyl- 2-butene-1,4-diyl or xylyldiyl.

Also very preferred are metal complexes and their heteroatom-containing ligands in which Z is -Z ^* -Y-, Z ^* is bonded to _Cp , Y is bonded to M, and

Y is -O-, -S-, -NR ^* -, -PR ^* -;

Z ^* for SiR ^* ₂ , CR ^* ₂ , SiR ^* ₂ , SiR ^* ₂ , CR ^* ₂ , CR ^* ₂ , CR ^* =CR ^* , CR*2, SiR ^* ₂ , CR ^* ₂ , SiR ^* ₂ ^, CR ^* _{2 ,} SiR ^* ₂ CR ^* ₂ SiR ^* ₂ , CR ^* ₂ CR ^* ₂ SiR ^* ₂ , CR ^* ₂ CR ^* ₂ CR ^* ₂ , or GeR ^* ₂ ; and

R ^* are independently hydrogen, or groups selected from hydrocarbyl, hydrocarbyloxy, silyl, haloalkyl, haloaryl, and combinations thereof, said R ^* having up to 20 non-hydrogen atoms, and optionally Two R ^* from Z (when ^R* is not hydrogen), or one R ^* from Z and one R ^* group from Y form a ring system;

where p is 1, q is 0, M is in the apparent oxidation state of +3, and X is 2-(N,N-methyl)aminobenzyl, 2-(N,N-methylaminomethyl)phenyl , Allyl, Methallyl, Trimethylsilylallyl.

Also very preferred are metal complexes and their heteroatom-containing ligands in which Z is -Z ^* -Y-, Z ^* is bonded to _Cp , Y is bonded to M, and

Y is -O-, -S-, -NR ^* -, -PR ^* -;

Z ^* for SiR ^* ₂ , CR ^* ₂ , SiR ^* ₂ , SiR ^* ₂ , CR ^* ₂ , CR ^* ₂ , CR ^* =CR ^* , CR*2, SiR ^* ₂ , CR ^* ₂ , SiR ^* ₂ ^, CR ^* _{2 ,} SiR ^* ₂ CR ^* ₂ SiR ^* ₂ , CR ^* ₂ CR ^* ₂ SiR ^* ₂ , CR ^* ₂ CR ^* ₂ CR ^* ₂ , or GeR ^* ₂ ; and

R ^* are independently hydrogen, or groups selected from hydrocarbyl, hydrocarbyloxy, silyl, haloalkyl, haloaryl, and combinations thereof, said R ^* having up to 20 non-hydrogen atoms, and optionally Two R ^* from Z (when R ^* is not hydrogen), or one R ^* from Z and one R ^* group from Y form a ring system;

where p is 0, q is 1, M is in the apparent oxidation state of +2, and X is 1,4-diphenyl-1,3-butadiene, 1,3-pentadiene or 2,4-hexa Diene.

Various metals can be used to prepare the metal complexes of the present invention, suitable metals are metals selected from Groups 3 to 13 of the Periodic Table of the Elements, the Lanthanides or the Actinides, which metals are in the +2, +3 or +4 apparent oxidation state, more suitable metals are metals selected from Groups 3 to 13. Metal complexes of the present invention having somewhat different properties are those wherein M is a metal selected from Groups 3-6, 7-9 or 10-12 of the Periodic Table of the Elements. Preferred are those wherein M is a metal selected from Group 4, preferably Ti, Zr or Hf, more preferably Ti and Zr. Ti is the most preferred metal, especially for use in complexes containing only one heteroatom-containing _Cp ligand of the present invention, while Zr is suitable for use with two _Cp ligands (at least one of which is a heteroatom-containing The metal is more preferred in the complex of the ligand).

In one embodiment, Ti is preferably in the +4 apparent oxidation state, or Ti is preferably in the +3 apparent oxidation state, more preferably in the +2 apparent oxidation state.

In another embodiment, Zr is preferably in the +4 apparent oxidation state, or in the +2 apparent oxidation state.

In another aspect of the invention, Y is preferably -NR ^* , and -NR ^* is more preferably those groups wherein R ^* is a group having an N-bonded primary or secondary carbon atom. Particularly preferred are those wherein R ^* is cyclohexyl or isopropyl.

Illustrative examples of metal derivatives that can be used in the practice of this invention include:

2-N-[heteroatom]tert-butylamino-indenyl complexes:

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)- 1H-inden-1-yl)silane ammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-piperidinyl)- 1H-inden-1-yl)silane ammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(hexahydro-1H-azepine In-1-yl)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(hexahydro-1(2H) -azocinyl)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(octahydro-1H-azo Nin-1-yl)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(octahydro-1(2H) -azecinyl)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)(N-(1,1-dimethylethyl)-1,1- Dimethyl-1-(silylammine(2-)-N)dimethyltitanium

(1,2,3,3a,7a-η)-2-(diethylamino)-1H-inden-1-yl)(N-(1,1-dimethylethyl)-1,1- Dimethyl-1-(silylammine(2-)-N)dimethyltitanium

(1,2,3,3a,7a-η)-2-(dipropylamino)-1H-inden-1-yl)(N-(1,1-dimethylethyl)-1,1- Dimethyl-1-(silylammine(2-)-N)dimethyltitanium

(1,2,3,3a,7a-η)-2-(dibutylamino)-1H-inden-1-yl)(N-(1,1-dimethylethyl)-1,1- Dimethyl-1-(silylammine(2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(ethylmethylamino)- 1H-inden-1-yl)silane ammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(methylphenylamino)- 1H-inden-1-yl)silane ammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(methyl(benzyl) Amino)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-((1,1-(two Methylethyl)methylamino)-1H-inden-1-yl)silaneamine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(methyl(1-methyl Ethyl)amino)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(diphenylphosphino)- 1H-inden-1-yl)silane ammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(dimethylphosphino)- 1H-inden-1-yl)silane ammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(methylphenylphosphino) -1H-inden-1-yl)silaneamine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(diethylphosphino)- 1H-inden-1-yl)silane ammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(bis(1-methylethyl Base) phosphino) -1H-inden-1-yl) silane ammine (2-) -N) dimethyl titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-methoxy-1H-indene- 1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-ethoxy-1H-indene- 1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-propoxy-1H-indene- 1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-butoxy-1H-indene- 1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-((1,1-dimethyl Ethyl)oxy)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(trimethylsilyloxy )-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(((1,1-di Methylethyl)dimethylsilyl)oxy)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-methylethoxy )-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-phenoxy-1H-indene- 1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(phenylthio)-1H- Inden-1-yl)silane ammine (2-)-N)titanium dimethyl

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(methylthio)-1H- Inden-1-yl)silane ammine (2-)-N)titanium dimethyl

3-Methyl-2-N-[heteroatom]tert-butylamino-indenyl complex:

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(1- Pyrrolidinyl)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(1- Piperidinyl)-1H-inden-1-yl)silaneamine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(hexahydro -1H-azepin-1-yl)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(hexahydro -1(2H)-azocinyl)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(octahydro -1H-azonin-1-yl)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(octahydro -1(2H)-azecinyl)-1H-inden-1-yl)silane ammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(dimethyl Amino)-1H-inden-1-yl)silaneammine (2-)-N)titanium dimethyl

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(diethyl Amino)-1H-inden-1-yl)silaneammine (2-)-N)titanium dimethyl

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(dipropyl Amino)-1H-inden-1-yl)silaneammine (2-)-N)titanium dimethyl

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(dibutyl Amino)-1H-inden-1-yl)silaneammine (2-)-N)titanium dimethyl

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(ethyl Methylamino)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(methyl Phenylamino)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(methyl (Benzyl)amino)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-((1 , 1-(dimethylethyl)methylamino)-1H-inden-1-yl)silaneamine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(methyl (1-methylethyl)amino)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(diphenyl Phosphino)-1H-inden-1-yl)silaneammine (2-)-N)titanium dimethyl

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(dimethyl Phosphino)-1H-inden-1-yl)silaneammine (2-)-N)titanium dimethyl

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(methyl Phenylphosphino)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(diethyl Phosphino)-1H-inden-1-yl)silaneammine (2-)-N)titanium dimethyl

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(bis( 1-methylethyl)phosphino)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-methoxy -1H-inden-1-yl)silaneamine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-ethoxy -1H-inden-1-yl)silaneamine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-propoxy -1H-inden-1-yl)silaneamine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-butoxy -1H-inden-1-yl)silaneamine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-((1 , 1-dimethylethyl)oxy)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(trimethyl Silyloxy)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-((( 1,1-Dimethylethyl)dimethylsilyl)oxy)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(1- Methylethoxy)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-phenoxy -1H-inden-1-yl)silaneamine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(phenylthio Base)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(methylthio Base)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

2-N-Heteroatom[amino]-indenyl complexes

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those wherein N-(1,1-dimethylethyl) is replaced by N-cyclohexyl, as illustrated by the following compounds :

(N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)-1H-inden-1-yl)silane Ammine (2-)-N)dimethyltitanium

(N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-piperidinyl)-1H-inden-1-yl)silane Ammine (2-)-N)dimethyltitanium

(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)(N-cyclohexyl-1,1-dimethyl-1-(silylamino (2-)-N)Dimethyltitanium

(1,2,3,3a,7a-η)-2-(diethylamino)-1H-inden-1-yl)(N-cyclohexyl-1,1-dimethyl-1-(silylamino (2-)-N)Dimethyltitanium

(N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(ethylmethylamino)-1H-indene- 1-yl)silaneammine (2-)-N)dimethyltitanium

(N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(methylphenylamino)-1H-indene- 1-yl)silaneammine (2-)-N)dimethyltitanium

(N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-methoxy-1H-inden-1-yl)silaneamine (2 -)-N)Dimethyltitanium

(N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-((1,1-dimethylethyl)oxy)-1H -inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(trimethylsilyloxy)-1H-inden-1-yl ) silane ammine (2-)-N) dimethyl titanium

(N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(dimethylamino)-1H-indene-1 -yl)silane ammine (2-)-N)dimethyltitanium

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those wherein N-(1,1-dimethylethyl) is replaced by N-methyl, as illustrated by the following compounds :

(N-methyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)-1H-inden-1-yl)silane Ammine (2-)-N)dimethyltitanium

(N-methyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-piperidinyl)-1H-inden-1-yl)silane Ammine (2-)-N)dimethyltitanium

(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)(N-methyl-1,1-dimethyl-1-(silylamino (2-)-N)Dimethyltitanium

(1,2,3,3a,7a-η)-2-(diethylamino)-1H-inden-1-yl)(N-methyl-1,1-dimethyl-1-(silylamino (2-)-N)Dimethyltitanium

(N-methyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(ethylmethylamino)-1H-indene- 1-yl)silaneammine (2-)-N)dimethyltitanium

(N-methyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(methylphenylamino)-1H-indene- 1-yl)silaneammine (2-)-N)dimethyltitanium

(N-Methyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-methoxy-1H-inden-1-yl)silaneamine (2 -)-N)Dimethyltitanium

(N-methyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-((1,1-dimethylethyl)oxy)-1H -inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-methyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(trimethylsilyloxy)-1H-inden-1-yl ) silane ammine (2-)-N) dimethyl titanium

(N-methyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(dimethylamino)-1H-indene-1 -yl)silane ammine (2-)-N)dimethyltitanium

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those wherein N-(1,1-dimethylethyl) is replaced by N-ethyl, as illustrated by the following compounds :

(N-ethyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)-1H-inden-1-yl)silane Ammine (2-)-N)dimethyltitanium

(N-Ethyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-piperidinyl)-1H-inden-1-yl)silane Ammine (2-)-N)dimethyltitanium

(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)(N-ethyl-1,1-dimethyl-1-(silylamino (2-)-N)Dimethyltitanium

(1,2,3,3a,7a-η)-2-(diethylamino)-1H-inden-1-yl)(N-ethyl-1,1-dimethyl-1-(silylamino (2-)-N)Dimethyltitanium

(N-ethyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(ethylmethylamino)-1H-indene- 1-yl)silaneammine (2-)-N)dimethyltitanium

(N-ethyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(methylphenylamino)-1H-indene- 1 base) silane ammine (2-)-N) dimethyl titanium

(N-Ethyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-methoxy-1H-inden-1-yl)silaneamine (2 -)-N)Dimethyltitanium

(N-ethyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-((1,1-dimethylethyl)oxy)-1H -inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-ethyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(trimethylsilyloxy)-1H-inden-1-yl ) silane ammine (2-)-N) dimethyl titanium

(N-ethyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(dimethylamino)-1H-indene-1 -yl)silane ammine (2-)-N)dimethyltitanium

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those wherein N-(1,1-dimethylethyl) is replaced by N-phenyl, as illustrated by the following compounds :

(1,1-Dimethyl-N-phenyl-1-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)-1H-inden-1-yl)silane Ammine (2-)-N)dimethyltitanium

(1,1-Dimethyl-N-phenyl-1-((1,2,3,3a,7a-η)-2-(1-piperidinyl)-1H-inden-1-yl)silane Ammine (2-)-N)dimethyltitanium

(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)(1,1-dimethyl-N-phenyl-1-(silylamino (2-)-N)Dimethyltitanium

(1,2,3,3a,7a-η)-2-(diethylamino)-1H-inden-1-yl)(1,1-dimethyl-N-phenyl-1-(silylamino (2-)-N)Dimethyltitanium

(1,1-Dimethyl-N-phenyl-1-((1,2,3,3a,7a-η)-2-(ethylmethylamino)-1H-inden-1-yl)silane Ammine (2-)-N)dimethyltitanium

(1,1-Dimethyl-N-phenyl-1-((1,2,3,3a,7a-η)-2-(methylphenylamino)-1H-inden-1-yl)silane Ammine (2-)-N)dimethyltitanium

(1,1-Dimethyl-N-phenyl-1-((1,2,3,3a,7a-η)-2-methoxy-1H-inden-1-yl)silaneamine (2 -)-N)Dimethyltitanium

(1,1-dimethyl-N-phenyl-1-((1,2,3,3a,7a-η)-2-((1,1-dimethylethyl)oxy)-1H -inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(1,1-Dimethyl-N-phenyl-1-((1,2,3,3a,7a-η)-2-(trimethylsilyloxy)-1H-inden-1-yl ) silane ammine (2-)-N) dimethyl titanium

(1,1-Dimethyl-N-phenyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(dimethylamino)-1H-indene-1 -yl)silane ammine (2-)-N)dimethyltitanium

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those wherein N-(1,1-dimethylethyl) is replaced by N-benzyl, as illustrated by the following compounds of:

(1,1-Dimethyl-N-(phenylmethyl)-1-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)-1H-indene-1- base) silane ammine (2-)-N) dimethyl titanium

(1,1-Dimethyl-N-(benzyl)-1-((1,2,3,3a,7a-η)-2-(1-piperidinyl)-1H-indene-1- base) silane ammine (2-)-N) dimethyl titanium

(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)(1,1-dimethyl-N-(benzyl)-1- (Silaneammine(2-)-N)dimethyltitanium

(1,2,3,3a,7a-η)-2-(diethylamino)-1H-inden-1-yl)(1,1-dimethyl-N-(benzyl)-1- (Silaneammine(2-)-N)dimethyltitanium

(1,1-Dimethyl-N-(phenylmethyl)-1-((1,2,3,3a,7a-η)-3-methyl-2-(ethylmethylamino)-1H -inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(1,1-Dimethyl-N-(phenylmethyl)-1-((1,2,3,3a,7a-η)-3-methyl-2-(methylphenylamino)-1H -inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(1,1-Dimethyl-N-(phenylmethyl)-1-((1,2,3,3a,7a-η)-3-methyl-2-methoxy-1H-indene-1 -yl)silane ammine (2-)-N)dimethyltitanium

(1,1-Dimethyl-N-(phenylmethyl)-1-((1,2,3,3a,7a-η)-3-methyl-2-((1,1-dimethyl Ethyl)oxy)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(1,1-Dimethyl-N-(phenylmethyl)-1-((1,2,3,3a,7a-η)-3-methyl-2-(trimethylsilyloxy) -1H-inden-1-yl)silaneamine (2-)-N)dimethyltitanium

(1,1-Dimethyl-N-(phenylmethyl)-1-((1,2,3,3a,7a-η)-3-methyl-2-(dimethylamino)-1H- Inden-1-yl)silane ammine (2-)-N)titanium dimethyl

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those wherein N-(1,1-dimethylethyl) is replaced by N-cyclododecyl, as follows Compound Description:

(N-cyclododecyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)-1H-indene-1- base) silane ammine (2-)-N) dimethyl titanium

(N-cyclododecyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-piperidinyl)-1H-indene-1- base) silane ammine (2-)-N) dimethyl titanium

(N-cyclododecyl-1,1-dimethyl-1-(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl) Silane ammine (2-)-N)dimethyltitanium

(N-cyclododecyl-1,1-dimethyl-1-(1,2,3,3a,7a-η)-2-(diethylamino)-1H-inden-1-yl) Silane ammine (2-)-N)dimethyltitanium

(N-cyclododecyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(ethylmethylamino)-1H -inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-cyclododecyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(methylphenylamino)-1H -inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-Cyclododecyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-methoxy-1H-inden-1-yl)silylamine (2-)-N)Dimethyltitanium

(N-cyclododecyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-((1,1-dimethylethyl)oxy )-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-cyclododecyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(trimethylsilyloxy)-1H-indene- 1-yl)silaneammine (2-)-N)dimethyltitanium

(N-cyclododecyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(dimethylamino)-1H- Inden-1-yl)silane ammine (2-)-N)titanium dimethyl

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those in which N-(1,1-dimethylethyl) is replaced by N-methylethyl, such as the following compounds Explained:

(1,1-Dimethyl-N-(methylethyl)-1-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)-1H-indene-1 -yl)silane ammine (2-)-N)dimethyltitanium

(1,1-Dimethyl-N-(methylethyl)-1-((1,2,3,3a,7a-η)-2-(1-piperidinyl)-1H-indene-1 -yl)silane ammine (2-)-N)dimethyltitanium

(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)(1,1-dimethyl-N-(methylethyl)-1 -(Silaneammine(2-)-N)dimethyltitanium

(1,2,3,3a,7a-η)-2-(diethylamino)-1H-inden-1-yl)(1,1-dimethyl-N-(methylethyl)-1 -(Silaneammine(2-)-N)dimethyltitanium

(1,1-Dimethyl-N-(methylethyl)-1-((1,2,3,3a,7a-η)-3-methyl-2-(ethylmethylamino)- 1H-inden-1-yl)silane ammine (2-)-N)dimethyltitanium

(1,1-Dimethyl-N-(methylethyl)-1-((1,2,3,3a,7a-η)-3-methyl-2-(methylphenylamino)- 1H-inden-1-yl)silane ammine (2-)-N)dimethyltitanium

(1,1-Dimethyl-N-(methylethyl)-1-((1,2,3,3a,7a-η)-2-methoxy-1H-inden-1-yl)silane Ammine (2-)-N)dimethyltitanium

(1,1-dimethyl-N-(methylethyl)-1-((1,2,3,3a,7a-n)-2-((1,1-dimethylethyl)oxy Base)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(1,1-Dimethyl-N-(methylethyl)-1-((1,2,3,3a,7a-η)-2-(trimethylsilyl)oxy)-1H- Inden-1-yl)silane ammine (2-)-N)titanium dimethyl

(1,1-Dimethyl-N-(methylethyl)-1-((1,2,3,3a,7a-η)-3-methyl-2-(dimethylamino)-1H -inden-1-yl)silaneammine (2-)-N)dimethyltitanium

2-N-[Heteroatom][Amino]TiX ₂ -Indenyl Complexes

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those in which the two methyl groups bonded to the titanium atom are replaced by chlorine, as illustrated by the following compounds:

Dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl )-1H-inden-1-yl)silane ammine (2-)-N)titanium

Dichloro(N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-piperidinyl)-1H-inden-1-yl ) silane ammine (2-)-N) titanium

Dichloro(N-methyl-1,1-dimethyl-1-(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)silane Amine (2-)-N)titanium

Dichloro(N-methyl-1,1-dimethyl-1-(1,2,3,3a,7a-η)-2-(diethylamino)-1H-inden-1-yl)silane Amine (2-)-N) titanium

Dichloro(N-ethyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(ethylmethylamino)-1H- Inden-1-yl)silaneammine(2-)-N)titanium

Dichloro(1,1-dimethyl-N-phenyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(methylphenylamino)-1H- Inden-1-yl)silaneammine(2-)-N)titanium

Dichloro(1,1-dimethyl-N-(phenylmethyl)-1-((1,2,3,3a,7a-η)-3-methyl-2-(methylphenylamino) -1H-inden-1-yl)silane ammine (2-)-N)titanium

Dichloro(N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(methylphenylamino)-1H- Inden-1-yl)silaneammine(2-)-N)titanium

Dichloro(N-methyl-1,1-dimethyl-1-(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)silane Amine (2-)-N)titanium

Dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-methoxy-1H- Inden-1-yl)silaneammine(2-)-N)titanium

Dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(((1,1 -Dimethylethyl)dimethylsilyl)oxy)-1H-inden-1-yl)silaneammine (2-)-N)titanium

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those in which the two methyl groups bonded to the titanium atom are replaced by benzyl groups, as illustrated by the following compounds:

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)- 1H-inden-1-yl)silaneammine(2-)-N)bis(benzyl)titanium

(N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-piperidinyl)-1H-inden-1-yl)silane Ammine (2-)-N)bis(benzyl)titanium

(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)(N-methyl-1,1-dimethyl-1-(silylamino (2-)-N)bis(benzyl)titanium

(1,2,3,3a,7a-η)-2-(diethylamino)-1H-inden-1-yl)(N-methyl-1,1-dimethyl-1-(silylamino (2-)-N)bis(benzyl)titanium

(N-ethyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(ethylmethylamino)-1H-indene- 1-yl)silane ammine (2-)-N)bis(benzyl)titanium

(1,1-Dimethyl-N-phenyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(methylphenylamino)-1H-indene- 1-yl)silane ammine (2-)-N)bis(benzyl)titanium

(1,1-Dimethyl-N-(phenylmethyl)-1-((1,2,3,3a,7a-η)-3-methyl-2-(methylphenylamino)-1H -inden-1-yl)silaneammine (2-)-N)bis(benzyl)titanium

(N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(methylphenylamino)-1H-indene- 1-yl)silane ammine (2-)-N)bis(benzyl)titanium

(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)(N-methyl-1,1-dimethyl-1-(silylamino (2-)-N)bis(benzyl)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-methoxy-1H-indene- 1-yl)silane ammine (2-)-N)bis(benzyl)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(((1,1-di Methylethyl)dimethylsilyl)oxy)-1H-inden-1-yl)silaneammine (2-)-N)bis(phenylmethyl)titanium

Among the above names naming 2-heteroatom-indenyl complexes, compounds of a similar scope are those in which the two methyl groups bonded to the titanium atom are replaced by (trimethylsilyl)methyl groups, as shown in the following Compound Description:

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)- 1H-inden-1-yl)silaneammine(2-)-N)bis((trimethylsilyl)methyl)titanium

(N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-piperidinyl)-1H-inden-1-yl)silane Ammine(2-)-N)bis((trimethylsilyl)methyl)titanium

(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)(N-methyl-1,1-dimethyl-1-(silylamino (2-)-N)bis((trimethylsilyl)methyl)titanium

(1,2,3,3a,7a-η)-2-(diethylamino)-1H-inden-1-yl)(N-methyl-1,1-dimethyl-1-(silylamino (2-)-N)bis((trimethylsilyl)methyl)titanium

(N-ethyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(ethylmethylamino)-1H-indene- 1-yl)silaneammine(2-)-N)bis((trimethylsilyl)methyl)titanium

(1,1-Dimethyl-N-phenyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(methylphenylamino)-1H-indene- 1-yl)silaneammine(2-)-N)bis((trimethylsilyl)methyl)titanium

(1,1-Dimethyl-N-(phenylmethyl)-1-((1,2,3,3a,7a-η)-3-methyl-2-(methylphenylamino)-1H -Inden-1-yl)silaneamine (2-)-N)bis((trimethylsilyl)methyl)titanium

(N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(methylphenylamino)-1H-indene- 1-yl)silaneammine(2-)-N)bis((trimethylsilyl)methyl)titanium

(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)(N-methyl-1,1-dimethyl-1-(silylamino (2-)-N)bis((trimethylsilyl)methyl)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-methoxy-1H-indene- 1-yl)silaneammine(2-)-N)bis((trimethylsilyl)methyl)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(((1,1-di Methylethyl)dimethylsilyl)oxy)-1H-inden-1-yl)silaneammine (2-)-N)bis((trimethylsilyl)methyl)titanium

Among the above names naming 2-heteroatom-indenyl complexes, compounds of a similar scope are those in which the two methyl groups bonded to the titanium atom are replaced by 2,2-dimethylpropyl groups, such as the following compounds Explained:

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)- 1H-inden-1-yl)silaneammine(2-)-N)bis(2,2-dimethylpropyl)titanium

(N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-piperidinyl)-1H-inden-1-yl)silane Ammine(2-)-N)bis(2,2-dimethylpropyl)titanium

(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)(N-methyl-1,1-dimethyl-1-(silylamino (2-)-N)bis(2,2-dimethylpropyl)titanium

(1,2,3,3a,7a-η)-2-(diethylamino)-1H-inden-1-yl)(N-methyl-1,1-dimethyl-1-(silylamino (2-)-N)bis(2,2-dimethylpropyl)titanium

(N-ethyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(ethylmethylamino)-1H-indene- 1-yl)silane ammine (2-)-N)bis(2,2-dimethylpropyl)titanium

(1,1-Dimethyl-N-phenyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(methylphenylamino)-1H-indene- 1-yl)silane ammine (2-)-N)bis(2,2-dimethylpropyl)titanium

(1,1-Dimethyl-N-(phenylmethyl)-1-((1,2,3,3a,7a-η)-3-methyl-2-(methylphenylamino)-1H -Inden-1-yl)silaneamine (2-)-N)bis(2,2-dimethylpropyl)titanium

(N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(methylphenylamino)-1H-indene- 1-yl)silane ammine (2-)-N)bis(2,2-dimethylpropyl)titanium

(N-Methyl-1,1-dimethyl-1-(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)(silylamino (2-)-N)bis(2,2-dimethylpropyl)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-methoxy-1H-indene- 1-yl)silane ammine (2-)-N)bis(2,2-dimethylpropyl)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(((1,1-di Methylethyl)dimethylsilyl)oxy)-1H-inden-1-yl)silaneammine (2-)-N)bis(2,2-dimethylpropyl)titanium

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those in which the two methyl groups bonded to the titanium atom are replaced by a 2-((dimethylamino)methyl)phenyl group Those compounds, as illustrated by the following compounds:

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

(N-cyclohexyl-1,1-dimethyl(2-((dimethylamino)methyl)phenyl)-1-((1,2,3,3a,7a-n)-2-( 1-piperidinyl)-1H-inden-1-yl)silaneammine (2-)-N)titanium

(2-((dimethylamino)methyl)phenyl)(N-methyl-1,1-dimethyl-1-(1,2,3,3a,7a-η)-2-(di Methylamino)-1H-inden-1-yl)silaneammine (2-)-N)titanium

(2-((dimethylamino)methyl)phenyl)(N-ethyl-1,1-dimethyl-1-(1,2,3,3a,7a-η)-3-methyl -2-(Ethylmethylamino)-1H-inden-1-yl)silaneammine (2-)-N)titanium

(2-((dimethylamino)methyl)phenyl)(1,1-dimethyl-N-phenyl-1-((1,2,3,3a,7a-η)-3-methyl Base-2-(methylphenylamino)-1H-inden-1-yl)silaneammine(2-)-N)titanium

(2-((dimethylamino)methyl)phenyl)(1,1-dimethyl-N-(phenylmethyl)-1-((1,2,3,3a,7a-η)- 3-Methyl-2-(methylphenylamino)-1H-inden-1-yl)silaneammine(2-)-N)titanium

(N-cyclohexyl-1,1-dimethyl(2-((dimethylamino)methyl)phenyl)-1-((1,2,3,3a,7a-n)-3-form Base-2-(methylphenylamino)-1H-inden-1-yl)silaneammine(2-)-N)titanium

(2-((dimethylamino)methyl)phenyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a , 7a-η)-2-methoxy-1H-inden-1-yl)silaneammine (2-)-N)titanium

(2-((dimethylamino)methyl)phenyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a , 7a-η)-2-(((1,1-dimethylethyl)dimethylsilyl)oxy)-1H-inden-1-yl)silaneammine (2-)-N) titanium

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those in which the two methyl groups bonded to the titanium atom are replaced by a 2-((dimethylamino)phenyl)methyl group Those compounds, as illustrated by the following compounds:

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

(N-cyclohexyl-1,1-dimethyl(2-((dimethylamino)phenyl)methyl)-1-((1,2,3,3a,7a-n)-2-( 1-piperidinyl)-1H-inden-1-yl)silaneammine (2-)-N)titanium

(2-((dimethylamino)phenyl)methyl)(N-methyl-1,1-dimethyl-1-(1,2,3,3a,7a-η)-2-(di Methylamino)-1H-inden-1-yl)silaneammine (2-)-N)titanium

(2-((dimethylamino)phenyl)methyl)(N-ethyl-1,1-dimethyl-1-(1,2,3,3a,7a-η)-3-methyl -2-(Ethylmethylamino)-1H-inden-1-yl)silaneammine (2-)-N)titanium

(2-((dimethylamino)phenyl)methyl)(1,1-dimethyl-N-phenyl-1-((1,2,3,3a,7a-η)-3-form Base-2-(methylphenylamino)-1H-inden-1-yl)silaneammine(2-)-N)titanium

(2-((dimethylamino)phenyl)methyl)(1,1-dimethyl-N-(phenylmethyl)-1-((1,2,3,3a,7a-η)- 3-Methyl-2-(methylphenylamino)-1H-inden-1-yl)silaneammine(2-)-N)titanium

(N-cyclohexyl-1,1-dimethyl(2-((dimethylamino)phenyl)methyl)-1-((1,2,3,3a,7a-n)-3-methyl Base-2-(methylphenylamino)-1H-inden-1-yl)silaneammine(2-)-N)titanium

(2-((dimethylamino)phenyl)methyl)(N-methyl-1,1-dimethyl-1-(1,2,3,3a,7a-η)-2-(di Methylamino)-1H-inden-1-yl)silaneammine (2-)-N)titanium

(2-((dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a , 7a-η)-2-methoxy-1H-inden-1-yl)silaneammine (2-)-N)titanium

(2-((dimethylamino)phenyl)methyl)(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a , 7a-η)-2-(((1,1-dimethylethyl)dimethylsilyl)oxy)-1H-inden-1-yl)silaneammine (2-)-N) titanium

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those in which the two methyl groups bonded to the titanium atom are π-bonded by 1,4-diphenyl-1,3-butane Those compounds in which the diene is substituted, as illustrated by the following compounds:

(1,1'-(η ⁴ -1,3-butadiene-1,4-yl)bis(benzene)(N-(1,1-dimethylethyl)-1,1-dimethyl Base-1-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)-1H-inden-1-yl)silaneammine (2-)-N)titanium

(1,1'-(η ⁴ -1,3-butadiene-1,4-diyl)bis(benzene)(N-cyclohexyl-1,1-dimethyl-1-((1,2 , 3,3a,7a-η)-2-(1-piperidinyl)-1H-inden-1-yl)silaneammine (2-)-N)titanium

(1,1'-(η ⁴ -1,3-butadiene-1,4-diyl)bis(benzene)(N-methyl-1,1-dimethyl-1-(1,2, 3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)silaneammine (2-)-N)titanium

(1,1'-(η ⁴ -1,3-butadiene-1,4-diyl)bis(benzene)(N-methyl-1,1-dimethyl-1-(1,2, 3,3a,7a-η)-2-(diethylamino)-1H-inden-1-yl)silaneammine (2-)-N)titanium

(1,1'-(η ⁴ -1,3-butadiene-1,4-diyl)bis(benzene)(N-ethyl-1,1-dimethyl-1-(1,2, 3,3a,7a-η)-3-methyl-2-(ethylmethylamino)-1H-inden-1-yl)silaneammine (2-)-N)titanium

(1,1'-(η ⁴ -1,3-butadiene-1,4-diyl)bis(benzene)(1,1-dimethyl-N-phenyl)-1-((1, 2,3,3a,7a-η)-3-methyl-2-(methylphenylamino)-1H-inden-1-yl)silaneammine (2-)-N)titanium

(1,1'-(η ⁴ -1,3-butadiene-1,4-diyl)bis(benzene)(1,1-dimethyl-N-(benzyl)-1-(( 1,2,3,3a,7a-η)-3-methyl-2-(methylphenylamino)-1H-inden-1-yl)silaneammine (2-)-N)titanium

(1,1'-(η ⁴ -1,3-butadiene-1,4-diyl)bis(benzene)(N-cyclohexyl-1,1-dimethyl-1-((1,2 , 3,3a,7a-η)-3-methyl-2-(methylphenylamino)-1H-inden-1-yl)silaneammine (2-)-N)titanium

(1,1'-(η ⁴ -1,3-butadiene-1,4-diyl)bis(benzene)(N-methyl-1,1-dimethyl-1-(1,2, 3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)silaneammine (2-)-N)titanium

(1,1'-(η ⁴ -1,3-butadiene-1,4-diyl)bis(benzene)(N-(1,1-dimethylethyl)-1,1-dimethyl Base-1-((1,2,3,3a,7a-η)-2-methoxy-1H-inden-1-yl)silaneamine (2-)-N)titanium

(1,1'-(η ⁴ -1,3-butadiene-1,4-diyl)bis(benzene)(N-(1,1-dimethylethyl)-1,1-dimethyl Base-1-((1,2,3,3a,7a-η)-2-(((1,1-dimethylethyl)dimethylsilyl)oxy)-1H-indene-1 -yl)silane ammine (2-)-N)titanium

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those in which the two methyl groups bonded to the titanium atom are replaced by π-bonded 1,3-pentadiene, such as The following compounds are illustrated:

(N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-piperidinyl)-1H-inden-1-yl)silane Ammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(N-ethyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(ethylmethylamino)-1H-indene- 1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(1,1-Dimethyl-N-phenyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(methylphenylamino)-1H-indene- 1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(1,1-Dimethyl-N-(phenylmethyl)-1-((1,2,3,3a,7a-η)-3-methyl-2-(methylphenylamino)-1H -inden-1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(methylphenylamino)-1H-indene- 1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)- 1H-inden-1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-piperidinyl)- 1H-inden-1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(hexahydro-1H-azepine Insin-1-yl)-1H-inden-1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(hexahydro-1(2H) -Azaoctinoyl)-1H-inden-1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(octahydro-1H-azo Nin-1-yl)-1H-inden-1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(octahydro-1(2H) -azecinyl)-1H-inden-1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)(N-(1,1-dimethylethyl)-1,1- Dimethyl-1-(silaneammine(2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(1,2,3,3a,7a-η)-2-(diethylamino)-1H-inden-1-yl)(N-(1,1-dimethylethyl)-1,1- Dimethyl-1-(silaneammine(2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(1,2,3,3a,7a-η)-2-(dipropylamino)-1H-inden-1-yl)(N-(1,1-dimethylethyl)-1,1- Dimethyl-1-(silaneammine(2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(1,2,3,3a,7a-η)-2-(dibutylamino)-1 H-inden-1-yl)(N-(1,1-dimethylethyl)-1,1 -Dimethyl-1-(silaneammine(2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(ethylmethylamino)- 1H-inden-1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(methylphenylamino)- 1H-inden-1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(methyl(benzyl) Amino)-1H-inden-1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadienyl)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-((1,1-(two Methylethyl)methylamino)-1H-inden-1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(methyl(1-methyl Ethyl)amino)-1H-inden-1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(diphenylphosphino)- 1H-inden-1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(dimethylphosphino)- 1H-inden-1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(methylphenylphosphino) -1H-inden-1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(diethylphosphino)- 1H-inden-1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(bis(1-methylethyl Base) phosphino)-1H-inden-1-yl) silaneammine (2-)-N) ((1,2,3,4-η)-1,3-pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-methoxy-1H-indene- 1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-ethoxy-1H-indene- 1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-propoxy-1H-indene- 1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-butoxy-1H-indene- 1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-((1,1-dimethyl Ethyl)oxy)-1H-inden-1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(trimethylsilyloxy )-1H-inden-1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(((1,1-di Methylethyl) dimethylsilyl) oxy) -1H-inden-1-yl) silane ammino (2-) -N) ((1,2,3,4-η)-1,3 -pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-methylethoxy )-1H-inden-1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-phenoxy-1H-indene- 1-yl)silaneammine (2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(phenylthio)-1H- Inden-1-yl)silaneammine(2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(methylthio)-1H- Inden-1-yl)silaneammine(2-)-N)((1,2,3,4-η)-1,3-pentadiene)titanium

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those in which the two methyl groups bonded to the titanium atom are replaced by π-bonded 2,4-hexadiene, such as The following compounds are illustrated:

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)- 1H-inden-1-yl)silaneammine (2-)-N)((1,2,3,4-η)-2,4-hexadiene)titanium

(N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-piperidinyl)-1H-inden-1-yl)silane Amine (2-)-N)((1,2,3,4-η)-2,4-hexadiene)titanium

(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)(N-methyl-1,1-dimethyl-1-(silylamino (2-)-N)((1,2,3,4-η)-2,4-hexadiene)titanium

(1,2,3,3a,7a-η)-2-(diethylamino)-1H-inden-1-yl)(N-methyl-1,1-dimethyl-1-(silylamino (2-)-N)((1,2,3,4-η)-2,4-hexadiene)titanium

(N-ethyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(ethylmethylamino)-1H-indene- 1-yl)silaneammine (2-)-N)((1,2,3,4-η)-2,4-hexadiene)titanium

(1,1-Dimethyl-N-phenyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(methylphenylamino)-1H-indene- 1-yl)silaneammine (2-)-)-((1,2,3,4-η)-2,4-hexadiene)titanium

(1,1-Dimethyl-N-(phenylmethyl)-1-((1,2,3,3a,7a-η)-3-methyl-2-(methylphenylamino)-1H -inden-1-yl)silaneammine (2-)-N)((1,2,3,4-η)-2,4-hexadiene)titanium

(N-cyclohexyl-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(methylphenylamino)-1H-indene- 1-yl)silaneammine (2-)-N)((1,2,3,4-η)-2,4-hexadiene)titanium

(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)(N-methyl-1,1-dimethyl-1-(silylamino (2-)-N)((1,2,3,4-,1)-2,4-hexadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-methoxy-1H-indene- 1-yl)silaneammine (2-)-N)((1,2,3,4-η)-2,4-hexadiene)titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(((1,1-di Methylethyl) dimethylsilyl) oxy) -1H-inden-1-yl) silane ammino (2-) -N) ((1,2,3,4-η)-2,4 -Hexadiene)titanium

2-N[Heteroatom]-amino-[bridged]-indenyl complexes

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those wherein the dimethylsilyl bridging group is replaced by a diphenylsilyl group, as illustrated by the following compounds:

(N-(1,1-dimethylethyl)-1,1-diphenyl-1-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)- 1H-inden-1-yl)silane ammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-diphenyl-1-((1,2,3,3a,7a-η)-2-(1-piperidinyl)- 1H-inden-1-yl)silane ammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-diphenyl-1-((1,2,3,3a,7a-η)-2-(dimethylamino)-1H -inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-diphenyl-1-((1,2,3,3a,7a-η)-3-methyl-2-methoxy -1H-inden-1-yl)silaneamine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-diphenyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(trimethyl Silyloxy)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those in which the dimethylsilyl bridging group is replaced by a diisopropoxysilyl group, as illustrated by the following compounds of:

(N-butyl-1,1-bis(1-methylethoxy))-1-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)-1H -inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-butyl-1,1-bis(1-methylethoxy))-1-((1,2,3,3a,7a-η)-2-(1-piperidinyl)-1H -inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-butyl-1,1-bis(1-methylethoxy))-1-((1,2,3,3a,7a-η)-2-(dimethylamino)-1H- Inden-1-yl)silane ammine (2-)-N)titanium dimethyl

(N-butyl-1,1-bis(1-methylethoxy))-1-((1,2,3,3a,7a-η)-3-methyl-2-methoxy- 1H-inden-1-yl)silane ammine (2-)-N)dimethyltitanium

(N-butyl-1,1-bis(1-methylethoxy))-1-((1,2,3,3a,7a-η)-3-methyl-2-(trimethyl Silyloxy)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those in which the dimethylsilyl bridging group is replaced by a dimethoxysilyl group, as illustrated by the following compounds :

(N-cyclohexyl-1,1-dimethoxy-1-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)-1H-inden-1-yl) Silane ammine (2-)-N)dimethyltitanium

(N-cyclohexyl-1,1-dimethoxy-1-((1,2,3,3a,7a-η)-2-(1-piperidinyl)-1H-inden-1-yl) Silane ammine (2-)-N)dimethyltitanium

((1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)(N-cyclohexyl-1,1-dimethoxy-1-silane Ammine (2-)-N)dimethyltitanium

(N-cyclohexyl-1,1-dimethoxy-1-((1,2,3,3a,7a-η)-3-methyl-2-methoxy-1H-inden-1-yl ) silane ammine (2-)-N) dimethyl titanium

(N-cyclohexyl-1,1-dimethoxy-1-((1,2,3,3a,7a-η)-3-methyl-2-(trimethylsilyloxy)-1H -inden-1-yl)silaneammine (2-)-N)dimethyltitanium

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those in which the dimethylsilyl bridging group is replaced by an ethoxymethylsilyl group, as illustrated by the following compounds of:

(N-cyclohexyl-1-ethoxy-1-methyl-1-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)-1H-indene-1- base) silane ammine (2-)-N) dimethyl titanium

(N-cyclohexyl-1-ethoxy-1-methyl-1-((1,2,3,3a,7a-η)-2-(1-piperidinyl)-1H-indene-1- base) silane ammine (2-)-N) dimethyl titanium

((1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)(N-cyclohexyl-1-ethoxy-1-methyl)- 1-Silaneammine (2-)-N)dimethyltitanium

(N-cyclohexyl-1-ethoxy-1-methyl-1-((1,2,3,3a,7a-η)-3-methyl-2-methoxy-1H-indene-1 -yl)silane ammine (2-)-N)dimethyltitanium

(N-cyclohexyl-1-ethoxy-1-methyl-1-((1,2,3,3a,7a-η)-3-methyl-2-(trimethylsilyloxy) -1H-inden-1-yl)silaneamine (2-)-N)dimethyltitanium

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those in which the dimethylsilyl bridging group is replaced by a methylphenylsilyl group, as illustrated by the following compounds :

(N-(1,1-dimethylethyl)-1-methyl-1-phenyl-1-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl )-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1-methyl-1-phenyl-1-((1,2,3,3a,7a-η)-2-(1-piperidinyl )-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)(N-(1,1-dimethylethyl)-1-methyl -1-phenyl-1-(silaneammine (2-)-N) dimethyltitanium

(N-(1,1-dimethylethyl)-1-methyl-1-phenyl-1-((1,2,3,3a,7a-η)-3-methyl-2-methyl Oxy-1H-inden-1-yl)silaneammine(2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1-methyl-1-phenyl-1-((1,2,3,3a,7a-η)-3-methyl-2-( Trimethylsilyloxy)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those in which the dimethylsilyl bridging group is replaced by an ethyl bridging group, as illustrated by the following compounds:

(N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)-1H-inden-1-yl) Ethamine (2-)-N) Dimethyltitanium

(N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-η)-2-(1-piperidinyl)-1H-inden-1-yl) Ethamine (2-)-N) Dimethyltitanium

(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)(N-(1,1-dimethylethyl)-2-(ethyl Ammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-η)-3-methyl-2-methoxy-1H-inden-1-yl ) ethylammine (2-)-N) dimethyl titanium

(N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-η)-3-methyl-2-(trimethylsilyloxy)-1H -Inden-1-yl)ethylamine(2-)-N)dimethyltitanium

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those in which the dimethylsilyl bridging group is replaced by a tetramethylethyl bridging group, such as the following compounds Explained:

(N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)-1H-inden-1-yl) Tetramethylethylamine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-η)-2-(1-piperidinyl)-1H-inden-1-yl) Tetramethylethylamine (2-)-N)dimethyltitanium

(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)(N-(1,1-dimethylethyl)-2-(tetra Methylethylamine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-η)-3-methyl-2-methoxy-1H-inden-1-yl )Tetramethylethylamine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-η)-3-methyl-2-(trimethylsilyloxy)-1H -inden-1-yl)tetramethylethylamine (2-)-N)titanium dimethyl

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those in which the dimethylsilyl bridging group is replaced by a propyl bridging group, as illustrated by the following compounds:

(N-(1,1-dimethylethyl)-3-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)-1H-inden-1-yl) Alanine(2-)-N)Dimethyltitanium

(N-(1,1-Dimethylethyl)-3-((1,2,3,3a,7a-η)-2-(1-piperidinyl)-1H-inden-1-yl) Alanine(2-)-N)Dimethyltitanium

(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)(N-(1,1-dimethylethyl)-2-(propane Ammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-3-((1,2,3,3a,7a-η)-3-methyl-2-methoxy-1H-inden-1-yl ) alanine (2-)-N) dimethyl titanium

(N-(1,1-dimethylethyl)-3-((1,2,3,3a,7a-η)-3-methyl-2-(trimethylsilyloxy)-1H -inden-1-yl)alanino(2-)-N)dimethyltitanium

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those wherein the dimethylsilyl bridging group is replaced by a methyl bridging group, as illustrated by the following compounds:

(N-(1,1-dimethylethyl)-3-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)-1H-inden-1-yl) Methamine (2-)-N) Dimethyltitanium

(N-(1,1-Dimethylethyl)-3-((1,2,3,3a,7a-η)-2-(1-piperidinyl)-1H-inden-1-yl) Methamine (2-)-N) Dimethyltitanium

(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)(N-(1,1-dimethylethyl)-2-(methyl Ammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-3-((1,2,3,3a,7a-η)-3-methyl-2-methoxy-1H-inden-1-yl ) methylamine (2-)-N) dimethyl titanium

(N-(1,1-dimethylethyl)-3-((1,2,3,3a,7a-η)-3-methyl-2-(trimethylsilyloxy)-1H -inden-1-yl)methylamine (2-)-N)dimethyltitanium

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those in which the dimethylsilyl bridging group is replaced by a dimethylmethyl bridging group, such as the following compounds Explained:

(N-(1,1-dimethylethyl)-3-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)-1H-inden-1-yl) Dimethylformazine (2-)-N)dimethyltitanium

(N-(1,1-Dimethylethyl)-3-((1,2,3,3a,7a-η)-2-(1-piperidinyl)-1H-inden-1-yl) Dimethylformazine (2-)-N)dimethyltitanium

(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)(N-(1,1-dimethylethyl)-2-(di Methylmethazine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-3-((1,2,3,3a,7a-η)-3-methyl-2-methoxy-1H-inden-1-yl )Dimethylmethamine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-3-((1,2,3,3a,7a-η)-3-methyl-2-(trimethylsilyloxy)-1H -inden-1-yl)dimethylmethamine (2-)-N)dimethyltitanium

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those in which a dimethylsilyl bridging group is replaced by a dimethylgermyl bridging group, such as The following compounds are illustrated:

(N-(1,1-dimethylethyl)-1-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)-1H-inden-1-yl) Dimethylgermane ammine (2-)-N)dimethyltitanium

(N-(1,1-Dimethylethyl)-1-((1,2,3,3a,7a-η)-2-(1-piperidinyl)-1H-inden-1-yl) Dimethylgermane ammine (2-)-N)dimethyltitanium

(1-(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)(N-(1,1-dimethylethyl)-2 -(Dimethylgermane ammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylgermane ammonium)-1-((1,2,3,3a,7a-η)-3-methyl-2-methoxy-1H-indene-1 -yl)dimethylgermaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1-((1,2,3,3a,7a-η)-3-methyl-2-(trimethylsilyloxy)-1H -inden-1-yl)dimethylgermane ammonium (2-)-N)dimethyltitanium

Within the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those wherein the dimethylsilyl bridging group is replaced by a tetramethyldisilyl bridging group, such as the following Compound Description:

(N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)-1H-inden-1-yl) Tetramethyldisilylamine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-η)-2-(1-piperidinyl)-1H-inden-1-yl) Tetramethyldisilylamine (2-)-N)dimethyltitanium

(1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)(N-(1,1-dimethylethyl)-2-(tetra (2-)-N)Dimethyltitanium methyldisilyl ammine

(N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-η)-3-methyl-2-methoxy-1H-inden-1-yl ) Tetramethyldisilazyl ammonium (2-)-N) dimethyltitanium

(N-(1,1-dimethylethyl)-2-((1,2,3,3a,7a-η)-3-methyl-2-(trimethylsilyloxy)-1H -inden-1-yl)tetramethyldisilylamine (2-)-N)dimethyltitanium

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those in which the dimethylsilyl bridging group is replaced by a (dimethylsilyl)methyl bridging group Compounds, as illustrated by the following compounds:

(N-(1,1-dimethylethyl)-1-(((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)-1H-inden-1-yl ) Dimethylsilyl) methylamine (2-)-N) titanium dimethyl

(N-(1,1-dimethylethyl)-1-(((1,2,3,3a,7a-η)-2-(1-piperidinyl)-1H-inden-1-yl ) Dimethylsilyl) methylamine (2-)-N) titanium dimethyl

(1-(((1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)dimethylsilyl)(N-(1,1 -Dimethylethyl)methamine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1-(((1,2,3,3a,7a-η)-3-methyl-2-methoxy-1H-indene-1- Base) dimethylsilyl) methylamine (2-)-N) dimethyl titanium

(N-(1,1-dimethylethyl)-1-(((1,2,3,3a,7a-η)-3-methyl-2-(trimethylsilyloxy)- 1H-inden-1-yl)dimethylsilyl)methylamine (2-)-N)dimethyltitanium

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those in which the dimethylsilyl bridging group is replaced by a (methyl)dimethylsilyl bridging group Compounds, as illustrated by the following compounds:

(N-(1,1-dimethylethyl)-1-(((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)-1H-inden-1-yl )methyl)dimethylsilylammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1-(((1,2,3,3a,7a-η)-2-(1-piperidinyl)-1H-inden-1-yl )methyl)dimethylsilylammine (2-)-N)dimethyltitanium

(1-(((1,2,3,3a,7a-η)-2-(dimethylamino)-1H-inden-1-yl)methyl)(N-(1,1-dimethyl Ethyl)-dimethylsilylammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1-(((1,2,3,3a,7a-η)-3-methyl-2-methoxy-1H-indene-1- Base) methyl) dimethyl silane ammine (2-)-N) dimethyl titanium

(N-(1,1-dimethylethyl)-1-(((1,2,3,3a,7a-η)-3-methyl-2-(trimethylsilyloxy)- 1H-inden-1-yl)methyl)dimethylsilylammine (2-)-N)dimethyltitanium

2-N-Heteroatom-amino-[indenyl] complexes

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those wherein the 2-heteroatom-indenyl moiety is replaced by an alkyl- or aryl-substituted 2-heteroatom-indenyl group, such as the following Compound Description:

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-5-ethyl-6-methyl- 2-(1-Pyrrolidinyl)-1H-inden-1-yl)silaneammine(2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-5-ethyl-6-methyl- 2-(1-piperidinyl)-1H-inden-1-yl)silaneammine(2-)-N)dimethyltitanium

(1-((1,2,3,3a,7a-η)-5-ethyl-6-methyl-2-(dimethylamino)-1H-inden-1-yl)(N-(1 , 1-dimethylethyl)-1,1-dimethylsilaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-5-ethyl-6-methyl- 3-Methyl-2-methoxy-1H-inden-1-yl)silaneamine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-5-ethyl-6-methyl- 3-Methyl-2-(trimethylsilyloxy)-1H-inden-1-yl)silaneamine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-4,6-dimethyl-2- (1-pyrrolidinyl)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-two-methylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-4,6-dimethyl-2 -(1-piperidinyl)-1H-inden-1-yl)silaneamine (2-)-N)dimethyltitanium

(1-((1,2,3,3a,7a-η)-4,6-dimethyl-2-(dimethylamino)-1H-inden-1-yl)(N-(1,1 -Dimethylethyl)-1,1-dimethylsilaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3,4,6-trimethyl- 2-Methoxy-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3,4,6-trimethyl- 2-(Trimethylsilyloxy)-1H-inden-1-yl)silaneammine(2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-4-phenyl-2-(1- Pyrrolidinyl)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-4-phenyl-2-(1- Piperidinyl)-1H-inden-1-yl)silaneamine (2-)-N)dimethyltitanium

(1-((1,2,3,3a,7a-η)-4-phenyl-2-(dimethylamino)-1H-inden-1-yl)(N-(1,1-dimethyl Ethyl)-1,1-dimethylsilaneammine (2-)-N)titanium dimethyl

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-4-phenyl-2-methoxy -1H-inden-1-yl)silaneamine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-4-phenyl-2-(trimethyl Silyloxy)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,9a-η)-5,6,7,8-tetrahydro -3,5,5,8,8-pentamethyl-2-(1-pyrrolidinyl)-1H-benzo(f)inden-1-yl)silaneammine(2-)-N)dimethyl Base Titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,9a-η)-5,6,7,8-tetrahydro -5,5,8,8-Tetramethyl-2-(1-pyrrolidinyl)-1H-benzo(f)inden-1-yl)silaneammine(2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,8a-eta)-1,5,6,7-tetrahydro -3-Methyl-2-(1-pyrrolidinyl)-s-dicyclopentadienyl acene (indacen)-1-yl)silaneammine (2-)-N-dimethyl-titanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,8a-eta)-, 5,6,7-tetrahydro- 2-(1-pyrrolidinyl)-s-dicyclopentadienenen-1-yl)silaneammine(2-)-N-dimethyl-titanium

In the above names naming 2-heteroatom-indenyl complexes, a similar range of compounds are those in which the 2-heteroatom indenyl moiety is replaced by an alkyl or aryl substituted cyclopentadienyl group, as illustrated by the following compounds of:

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-4,5,6,7-tetrahydro -2-(1-pyrrolidinyl)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-4,5,6,7-tetrahydro -2-(1-piperidinyl)-1H-inden-1-yl)silaneamine (2-)-N)dimethyltitanium

(1-((1,2,3,3a,7a-η)-4,5,6,7-tetrahydro-2-(dimethylamino)-1H-inden-1-yl)(N-( 1,1-Dimethylethyl)-1,1-dimethylsilaneammine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-4,5,6,7-tetrahydro -3-Methyl-2-methoxy-1H-inden-1-yl)silaneamine (2-)-N)dimethyltitanium

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-4,5,6,7-tetrahydro -3-Methyl-2-(trimethylsilyloxy)-1H-inden-1-yl)silaneamine (2-)-N)dimethyltitanium

(1-((1,2,3,4,5-η)-2-dimethylamino)-3-methyl-2,4-cyclopentadien-1-yl)-N-(1, 1-Dimethylethyl)-1,1-dimethylsilylammine (2-)-N)dimethyltitanium

(1-((1,2,3,4,5-η)-2-dimethylamino)-2,4-cyclopentadien-1-yl)-N-(1,1-dimethyl Ethyl)-1,1-dimethylsilylammine (2-)-N)dimethyltitanium

(1-((1,2,3,4,5-η)-3-dimethylamino)-3-methyl-2,4-cyclopentadien-1-yl)-N-cyclohexyl- 1,1-Dimethylsilylammine (2-)-N)dimethyltitanium

(1-((1,2,3,4,5-η)-2-dimethylamino)-2,4-cyclopentadien-1-yl)-N-cyclohexyl-1,1-di Methylsilylamine (2-)-N)dimethyltitanium

(1-((1,2,3,4,5-η)-2-methoxy)-3-methyl-2,4-cyclopentadien-1-yl)-N-(1,1 -Dimethylethyl)-1,1-dimethylsilaneammine (2-)-N)dimethyltitanium

(1-((1,2,3,4,5-η)-2-methoxy)-2,4-cyclopentadien-1-yl)-N-(1,1-dimethylethyl base)-1,1-dimethylsilylammine (2-)-N)dimethyltitanium

(1-((1,2,3,4,5-η)-2-methoxy)-3-methyl-2,4-cyclopentadien-1-yl)-N-cyclohexyl-1 , 1-dimethylsilylammine (2-)-N) dimethyltitanium

(1-((1,2,3,4,5-η)-2-methoxy)-2,4-cyclopentadien-1-yl)-N-cyclohexyl-1,1-dimethyl (2-)-N)dimethyltitanium silaneamine

(1-((1,2,3,3a,6a-η)-2-(dimethylamino)-1,4,5,6-tetrahydro-1-pentalyl)-N- (1,1-Dimethylethyl)1,1-dimethylsilaneammine (2-)-N)dimethyltitanium

(1-((1,2,3,3a,6a-η)-2-(dimethylamino)-1,4,5,6-tetrahydro-1-pentalyl)-N- Cyclohexyl) 1,1-dimethylsilane ammine (2-)-N) titanium dimethyl

(1-((1,2,3,3a,6a-η)-2-(methoxy)-1,4,5,6-tetrahydro-1-pentalenyl)-N-( 1,1-Dimethylethyl))1,1-Dimethylsilylamine (2-)-N)Dimethyltitanium

(1-((1,2,3,3a,6a-η)-2-(methoxy)-1,4,5,6-tetrahydro-1-pentalenyl)-N-( Cyclohexyl) 1,1-dimethylsilane ammine (2-)-N) titanium dimethyl

(1-((1,2,3,3a,6a-η)-2-(trimethylsilyloxy)-1,4,5,6-tetrahydro-1-pentalenyl) -N-(1,1-Dimethylethyl))(1,1-Dimethylsilylamine (2-)-N)dimethyltitanium

(1-((1,2,3,3a,6a-η)-2-(trimethylsilyloxy)-1,4,5,6-tetrahydro-1-pentalenyl) -N-cyclohexyl)1,1-dimethylsilaneammine (2-)-N)dimethyltitanium

(1-((1,2,3,3a,6a-η)-2-(trimethylsilyloxy)-1,4,5,6-tetrahydro-1-pentalenyl) -N-(1,1-dimethylethyl))1,1-dimethylsilaneammine (2-)-N)dimethyltitanium

(1-((1,2,3,3a,6a-η)-2-(trimethylsilyloxy)-1,4,5,6-tetrahydro-1-pentalenyl) -N-cyclohexyl)1,1-dimethylsilaneammine (2-)-N)dimethyltitanium

These complexes can be prepared by using well-known synthetic techniques. A reducing agent can optionally be used to produce a lower oxidation state complex. This method is disclosed in USSN 8/241,523 (filed May 13, 1994, published as WO 95/00526), the disclosure of which is incorporated herein by reference. The reaction is carried out in a suitable non-interfering solvent at a temperature of -100°C to 300°C, preferably -78 to 100°C, most preferably 0 to 50°C. The term "reducing agent" refers to a metal or compound which, under reducing conditions, reduces metal M from a higher oxidation state to a lower oxidation state. Examples of suitable metal reducing agents are alkali metals, alkaline earth metals, aluminum and zinc, alloys of alkali metals or alkaline earth metals such as sodium/mercury and sodium/potassium alloys. Examples of suitable reducing agent compounds are sodium naphthyl, potassium graphite, lithium alkyls, lithium or potassium alkadienyls; and Grignard reagents. The most preferred reducing agents are alkali metals or alkaline earth metals, especially lithium or magnesium metals.

Suitable reaction media for complex formation include aliphatic and aromatic hydrocarbons, ethers and cyclic ethers, especially branched chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof ; Cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; Aromatic and hydrocarbon-substituted aromatic compounds such as benzene, toluene and xylene, C _{1- 4} dialkyl ethers, C _1-4 dialkyl ether derivatives of (poly)alkylene glycols, and tetrahydrofuran. Mixtures of the aforementioned compounds are also suitable.

One synthesis of heteroatom-substituted cyclopentadienyl groups useful as precursors for constrained geometry catalyst systems (CGC) is given in Scheme 1 below, where:

a.) Excess amine, MeOH, 25°C (-H ₂ O);

b.) Cool excess amine (8eq), _TiCl4 (1eq) in _CH2Cl2 to 0°C, then add _ketone and warm to 25°C;

c.) Add 1.05eqn-BuLi/hexane at 25°C; d) Add 1.0-15eqCl-silane/THF at 25°C; e) Add 2.05eqn-BuLi/hexane at 25°C.

R, R', R", R'', R"" are each independently selected from H (except when directly connected to the N on the cyclopentadienyl), alkyl, cycloalkyl, aryl, alkaryl group, aralkyl group, but not limited to these groups. Scheme 1

Heteroatom-containing substituents have a nitrogen atom at the 2-position of the indenyl system. 2-Indanone is a common starting material for the conversion to the corresponding enamine, although the formation of the latter is not limited to the use of this compound. The enamines of indanones are generally formed by methods known in the art involving the condensation of secondary amines with ketones in absolute alcohol (U. Edlund Acta Chemica Scandinavica, 1974, 27, 4027 -4029). Enamines of 2-indanones are generally easier to form by amine condensation than 1-indanones. For more sterically hindered ketones such as 1-methyl-2-indanone or more volatile amines, stronger dehydrating agents such as titanium amidochloride (formed in situ from titanium tetrachloride and condensed amine) are preferred (R. Carlson, A. Nisson Scandinavian Journal of Chemistry B38, 1984, 49-53). These two methods have been used to produce enamines substituted at the 2-position of indene (the 1-position is usually bonded to silicon or other linking moiety of the latter compound). Another method for the preparation of enamines involves the electrophilic amination of carbanions such as indenyl lithium (E. Erdik, M. Ay, Chem. Rev., 1989, 89, 1947-1989).

For the subsequent formation of highly pure CGC ligands, the enamines prepared by these routes must be highly pure and free of ketones, Aldol by-products and heavier reaction tars that usually accompany product formation. None of the above routes provide a product that can be used directly without any purification. We have found that the use of flash-grade silica gel or alumina promotes rapid hydrolysis of enamines to free amines and ketones, an undesirable outcome. Although these compounds are very sensitive to water and air, such enamines can be purified by careful distillation or (occasionally) recrystallization. The rapid distillation of indenonenamines is especially necessary to prevent thermal polymerization at elevated temperatures in the still still. To obtain highly pure CGC-ligands, a suitable conversion of pure enamines into the corresponding anionic salts is required, since these enamines can also be photochemically sensitive.

2-indanones are preferred starting materials for CGC-ligands substituted by oxygen at the 2-position, as shown in Scheme 2 below, where: a.) alcohol, benzene is refluxed ( _-H2O ); b.) Add 1.05eqn-BuLi/hexane at 25°C; c) Add 1.0-1.5eq Cl-silane/THF at 25°C; d.) Add 2.05eqn-BuLi/hexane at 25°C;

R, R', R', R'', R"" are each independently selected from H (except oxygen), alkyl, cycloalkyl, aryl, alkaryl, aralkyl, but not limited to these groups group. Process 2

Enol ethers at this position can be prepared in particular by dehydration of suitable hemiketals formed in situ from indanones and alcohols in the presence of acid catalysts (L.A. Paquette, A. Varadrajan, E. Bey, J. , 6702-6708; W.E.Parham, C.D.Wright Journal of Organic Chemistry (J.Org.Chem.) 1957, 22, 1473-77), silyl enol ethers can be obtained by forming the enolate of -2-indanone and using, for example, tertiary Preparation by butyl-dimethylsilyl chloride quenching (R. Leino, H. Luttikhedde, C. E. Wilen, R. Sillanpa, J. H. Nasman, Organometallics, 1996, 15, 2450-2453). The enol ethers of indanones, like the enamine analogues, are also susceptible to hydrolysis and very sensitive to oxygen. For convenience, they are preferably converted to their corresponding anionic salts after purification.

Once purified, conversion of the enamine to the corresponding anionic salt can be carried out by reaction with a suitable concentration of base in a suitable non-interfering solvent. The solid anionic salt is typically filtered, washed and dried under suitable air-free, anhydrous conditions to give nearly quantitative yields. Likewise, the enol ethers of 2-indanones can be deprotonated into the corresponding anionic salts. For silyl enol ethers, the choice of base is more stringent, as certain bases, such as n-butyllithium, were found to cause desilylation, resulting in enolate anions (base attacking silyl groups).

The formation of heteroatom-substituted indene-based constrained geometry ligands (CGC ligands) was based on the anionic alkylation method described by Nickias and co-workers (Nickias, Peter N.; Devore, David D.; Wilson, David R., PCT International Application, WO 93/08199 A1 930429. CAN 119:160577; Carpenetti, Donald W.; Kloppenburg, Lioba; Kupec, Justin T.; Petersen, Jeffrey L.; ), wherein the cyclopentadienyl anion is reacted with an electrophile such as a halo-secondary alkylamine or a halo-secondary silylamine to give the corresponding cyclopentadienylalkylamine or cyclopentadienylsilylamine. Among halo-secondary alkylamines or halo-secondary silylamines include, for example, (tert-butyl)(chlorodimethylsilyl)amine, (tert-butyl)(chlorodimethylsilylmethyl) Amine, (tert-butyl)(bromomethyldimethylsilyl)amine, (tert-butyl)(2-chloroethyl)amine, (chlorodimethylsilyl)(phenyl)amine, ( Adamantyl)(chlorodiphenylsilyl)amine, (chlorodimethylsilyl)(cyclohexyl)amine, (benzyl)(chlorodimethylsilyl)amine and (tert-butyl) (Chloromethylphenylsilyl)amine. For example, by adding dropwise the lithium derivative of the anionic salt in THF to a molar excess of (tert-butyl)(chlorodimethylsilyl)amine in THF, followed by standard removal of lithium chloride and An excess of the electrophile usually provides the ligand for subsequent use without further purification. This so-called CGC-ligand can be converted into its insoluble dianionic salt by reacting the free base with 2 equivalents of a suitable concentration of base in a suitable non-interfering solvent.

A suitable non-interfering solvent in the context of the present invention is one that does not interfere with the formation of the desired product, or react unfavorably with the desired product. Such solvents suitable for the preparation of the anionic and dianionic salts of the present invention include, but are not limited to, aliphatic and aromatic hydrocarbons, especially straight and branched chain hydrocarbons such as butane, pentane, hexane, heptane, octane, decane, Alkanes, including their branched isomers and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and their compounds; aromatic and hydrocarbon-substituted aromatic Compounds such as benzene, toluene, xylene, ethylbenzene, diethylbenzene and mixtures thereof; ethers and cyclic ethers, especially C _1-6 dialkyl ethers such as diethyl ether, dibutyl ether and methyl tertiary ether Butyl ethers, C _1-6 dialkyl ether derivatives of (poly)alkylene glycols, such as dimethoxyethane and dioxane, and THF and mixtures thereof. Mixtures of the aforementioned solvents are also suitable.

Suitable concentrations of bases for preparing dianionic salts of the invention include hydrocarbyl salts of Group 1 and 2 metals, especially alkyl or aryl salts of lithium or magnesium, such as methyllithium, ethyllithium, n-butyllithium, sec- Butyllithium, tert-butyllithium, phenyllithium, methylmagnesium chloride, ethylmagnesium bromide, isopropylmagnesium chloride, dibutylmagnesium, (butyl)(ethyl)magnesium, dihexylmagnesium; Group 1 or Group 2 metals such as lithium, sodium, potassium, and magnesium; Group 1, 2, or 13 metal hydrides, such as lithium, sodium, potassium, or lithium aluminum hydride; Group 1 or 2 metal amides, Such as lithium diisopropylamide, lithium dimethylamide, lithium hexamethyldisilylamide, sodium amide and magnesium diisopropylamide.

Suitable concentrations of bases for use in preparing the anionic salts of this invention include the bases described above as well as Group 1 or 2 metal alkoxide complexes such as sodium ethoxide, sodium tert-butoxide, potassium butoxide and potassium pentyl.

Metallation of dianion salts can also be accomplished by methods known in the art. Reaction of dianionic salts in THF with _TiCl3 (THF) ₃ , followed by oxidation by dichloromethane or lead dichloride is a well-established method to provide titanium(IV) chloride complexes (J. Okuda, S. Verch, TPSpaniol, R. Sturmer, Chem. Ber., 1996, 129, 1429-1431, DDDevore EP 514, 828). The dichloride can be synthesized by reacting with a suitable silylation or hydrocarbylation agent, such as methyllithium, methylmagnesium chloride, benzylpotassium, allyllithium, trimethylsilylmethyllithium, neopentylbromide Magnesium oxide and phenyllithium undergo ligand exchange to be silylated or hydrocarbylated. A more complete description of suitable silylation or hydrocarbylating agents is set forth below.

A general method for the production of diene titanium(II) complexes from the corresponding titanium(IV) dichlorides has been disclosed by Devore and co-workers (D.D. Devore, F.J. Timmers, D.L. Hasha, R.K. Rosen, T.J. Marks, P.A. Deck, C.L. Stern , Organometallic Chemistry, 1995, 14, 3132-3134; D.D. Devore, F.J. Timmers, J.C. Stevens, R.D. Mussell, L.H. Crawford, D.R. Wilson, US 5,556,928). Thus, treatment of the dichloride with n-butyllithium in the presence of the appropriate diene produces similar titanium(II) diene complexes for heteroatom substituted systems.

The CGC metal(III) complexes of the present invention can be formed by one of a number of synthetic methods including: Dianion salts and trivalent metal salts such as Group 4 metal(III) can be carried out under air-free and anhydrous conditions. Halide or alcohol complex reaction, optionally followed by silylation or hydrocarbylation with a suitable silyl or hydrocarbylating agent, to form the corresponding CGC metal(III) halide, alkoxide, silyl or hydrocarbyl group of the present invention Complexes.

Another synthetic method of the present invention involves the reduction of a suitable CGC metal (IV) dihalide or dialkoxy complex, or first monosilylation or monohydrocarbylation, followed by the corresponding CGC (IV) silyl or The hydrocarbyl monohalide or monoalkoxy complex is reduced with a suitable reducing agent to form the corresponding CGC metal(III) chloride, alkoxide, silyl or hydrocarbyl complex.

A method found to be particularly suitable in the synthesis of the CGC metal(III) complexes of the present invention is the method disclosed by Wilson (D.R. Wilson US 5,504,224, 1996), which method is hereby incorporated by reference. For example, from a cyclopentadienyl-containing Group 4 metal complex in the +3 oxidation state, the cyclopentadienyl ligand can be substituted by a dianionic salt and/or by a (stabilizing) hydrocarbylating agent to obtain the present Invented CGC metal(III) ligands.

Suitable reducing agents for reducing the oxidation state of the metal of the CGC metal(IV) complex from +4 to +3 have been described above and include zinc, aluminum and magnesium in particular.

Suitable silylation and hydrocarbylation agents for use in the CGC metal(III) complexes and CGC metal(IV) complexes of the present invention include salts of Group 1, 2 or 13 metals of the following groups, preferably lithium, sodium, potassium , magnesium and aluminum salts: alkyl groups such as methyl, ethyl, propyl, butyl, neopentyl and hexyl; aryl groups such as phenyl, naphthyl and biphenyl; aralkyl groups such as benzyl , tolylmethyl, benzhydryl; alkaryl, such as tolyl and xylyl; allyl; silyl- or alkyl-substituted allyl, such as methallyl, trimethylsilyl aryl, dimethylallyl and trimethylallyl; trialkylsilyl, such as trimethylsilyl and triethylsilyl; trialkylsilylalkyl, Such as trimethylsilylmethyl; pentadienyl; alkyl- or silyl-substituted pentadienyl, such as methylpentadienyl, dimethylpentadienyl, trimethylsilyl ylpentadienyl, bis(trimethylsilyl)pentadienyl, cyclohexadienyl and dimethylcyclohexadienyl; dialkylaminoalkaryl, such as o-(N,N - dimethylaminomethyl)phenyl; and dialkylaminoaralkyl, such as o-(N,N-dimethylamino)benzyl. Preferred silylation and hydrocarbylation agents include trimethylaluminum, methyllithium, methylmagnesium chloride, neopentyllithium, trimethylsilylmethylmagnesium chloride and phenyllithium. Also included are stabilizing group-containing hydrocarbylating agents, particularly salts of stabilizing group-containing hydrocarbylating agents and stabilizing group-containing hydrocarbyl groups described in US 5,504,224, including, for example, potassium benzyl, 2 -(N,N-Dimethylamino)benzyllithium, allyllithium and dimethylpentadienylpotassium. Stabilizing groups are further described in US Serial No. 8003 (filed January 21, 1993, corresponding to WO 93/19104), incorporated herein by reference.

Preferred halides or alkoxides of metal(III) halide or alkoxide complexes and CGC metal(III) halide or alkoxide complexes include fluoride, chloride, bromide, iodide, methoxide, ethoxide, Isopropoxide, n-propoxide, butoxide and phenoxide. Preferred metal(III) halide or alkoxide complexes include titanium(III) chloride, titanium(III) ethoxide, titanium(III) bromide, titanium(III) isopropoxide, (dichloride)(isopropyl alkoxide) titanium(III), and the aforementioned Lewis base complexes, especially their ether complexes, especially their diethyl ether, tetrahydrofuran and ethylene glycol dimethyl ether complexes. Preferred cyclopentadienyl-containing Group 4 metal complexes in the +3 oxidation state include tricyclopentadienyl titanium, dicyclopentadienyl titanium chloride, dicyclopentadienyl titanium chloride, dicyclopentadienyl titanium Dienyl titanium bromide, dicyclopentadienyl isopropoxide titanium, cyclopentadienyl titanium dichloride, cyclopentadienyl diphenoxy titanium, cyclopentadienyl dimethanol titanium and bis(tri Methylsilyl)(tert-butyl)(cyclopentadienyl)zirconium chloride.

The ligand of the present invention is a cyclopentadienyl ligand containing 2-heteroatom substitution, wherein the ligand is in the following form:

(A) a free base with 2 protons capable of removal;

(B) dilithium salt;

(C) magnesium salt; or

(D) Mono- or disilylated dianions.

Synthetic production of the metal complexes of the present invention with the ligands of the present invention, or the use of metal complexes comprising a metal and 1 to 4 ligands from Groups 3 to 13, lanthanides or actinides of the periodic table of elements, also within the scope of the present invention.

The ligands of the present invention can be used in various forms, including salts with various groups attached at the Z position which, when synthesized, result in metal complexes in which the metal is Groups 3-16 of the Periodic Table or Lanthanum For metals of the metal complex, only 1 to 4 of these ligands are present in the metal complex, or coexist with other ligands. The synthesis method can be similar to the method discussed for the synthesis of the Group 4 metal complex of the present invention, or can be other various synthesis methods known in the art. These metal complexes are used as catalysts in various reactions including olefin polymerization.

Obviously, it is complicated and difficult to name these metal complexes, as well as neutral ligands and various intermediates, and there are various naming rules. Therefore, it is recommended to refer to the structural representation. Typically, the heteroatom is in the 2-position for bridged tethered geometry complexes or bis- _Cp complexes bridged at the 1-position. The structural representations given here should not be strictly literal interpretations in terms of bond order, bond length or strength. For example, x-ray data show that the NC _p bonds of some complexes are shorter than expected for single bonds, which suggests some double bond characteristics in the NC _p bonds.

Within the scope of the above discussion involving ligands, preferred ligands of the invention conform to the general formula:

Where x is 0 or 1, y is 0 or 1, z is 0 or 1, x+y is 0 or 1, x+z is 0 or 1, and other symbols are as defined above, wherein the dotted circle in the CP ring represents the double bond feature , partial double bond character or arene character (if appropriate) various possibilities, depending on the values of x, y and z.

The complexes are rendered catalytically active by combination with an activating co-catalyst or by using activation techniques. Activating cocatalysts useful herein include polymeric or oligomeric aluminoxanes, especially methylalumoxane, triisobutylaluminum-modified methylalumoxane, or isobutylaluminoxane; neutral Lewis acids such as C _1-45 hydrocarbyl substituted Group 13 compounds, especially tri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boron compounds and their halogenated (including perhalogenated) compounds having 1 to 15 carbon atoms in each hydrocarbyl or halogenated hydrocarbyl group substituted) derivatives, especially perfluorotri(aryl)borane compounds, most preferably tris(o-nonafluorobiphenyl)borane, tris(pentafluorophenyl)borane; non-polymeric compatible non-ligating Ion-forming compounds (including the use of these compounds under oxidizing conditions), especially ammonium, phosphonium, oxonium, carbonium, silium, or sulfonium salts using compatible non-coordinating anions, or compatible, non-coordinating anions ferrocenium; bulk electrolysis (explained in more detail below); and in combination with the activation co-catalysts and techniques described above. For different metal complexes, the above activation cocatalyst and activation technology have been disclosed in the following documents: EP-A-277,033, US-A-5,153,157, US-A-5,064,802, EP-A-468,651 (equivalent to US Serial No. 07/547,718), EP-A-520,732 (equivalent to US Serial No. 07/876,268) and EP-A-520,732 (equivalent to US Serial No. 07/884,966, filed May 1, 1992), these documents The disclosure is incorporated herein by reference.

Compositions of polymeric or oligomeric aluminoxanes with Lewis acids, especially trialkylaluminum compounds having 1 to 4 carbon atoms in each alkyl group and halogenated trialkylene compounds having 1 to 20 carbon atoms in each hydrocarbyl group (Hydrocarbyl)boron compounds, especially tris(pentafluorophenyl)borane, tris(o-nonafluorobiphenyl)borane, and compositions with mixtures of these neutral Lewis acids, and individual neutral Combinations of Lewis acids, especially tris(pentafluorophenyl)borane, with polymeric or oligomeric aluminoxanes are particularly suitable activating cocatalysts. It is an advantage of the present invention that it has been found that the most efficient catalyst activation using this tris(pentafluorophenyl)borane/aluminoxane mixture composition occurs when the amount of aluminoxane is reduced. Group 4 metal complex: tris(pentafluorophenyl)borane:aluminoxane preferably in a molar ratio of 1:1:1 to 1:5:5, more preferably 1:1:1.5 to 1:5:3 . The present invention surprisingly effectively produces olefin polymers with high catalytic efficiency using lower amounts of expensive aluminoxane cocatalysts. Furthermore, the polymers obtained have lower amounts of aluminum residues and therefore better transparency.

Suitable ion-forming compounds for use as cocatalysts in one embodiment of the present invention include cations which are Bronsted acids capable of donating a proton and compatible non-coordinating anions A ⁻ . The term "non-coordinating" as used herein refers to anions or species that do not coordinate to Group 4 metal-containing precursor complexes and catalyst derivatives derived therefrom, or only weakly coordinate to these complexes, whereby Retains enough to be readily displaced by neutral Lewis bases. A non-coordinating anion is in particular an anion which, when used as a charge-balancing anion in a cationic metal complex, does not transfer an anionic substituent or fragment thereof to said cation, thereby forming a neutral complex. "Compatible anion" means an anion that does not degrade to neutrality or interfere with the desired subsequent polymerization or other use of the complex when the initially formed complex decomposes.

Preferred anions are those containing a single complex comprising a charged metal or metalloid core which is capable of balancing the charge of the active catalyst species (metal cation) formed when the two components are combined. The anion should also be sufficiently readily displaced by olefins, dienes and acetylenically unsaturated compounds or other neutral Lewis bases such as ethers or nitriles. Suitable metals include, but are not limited to, aluminum, gold and platinum. Suitable metalloids include, but are not limited to, boron, phosphorus, and silicon. Anion-containing compounds, including complexes containing a single metal or metalloid atom, are of course well known, and in particular many compounds containing a single boron atom in the anion portion are commercially available.

Preferably these cocatalysts can be represented by the general formula:

(L ^* -H) _d ⁺ (A) ^{d -} where:

L ^* is a neutral Lewis base;

(L ^* -H) ⁺ is a Bronsted acid

(A) ^d- is a non-coordinating compatible anion with charge d-, and

d is an integer of 1 to 3.

(A) ^d- more preferably conforms to the general formula: [M'Q ₄ ] ^- ;

in:

M' is boron or aluminum in the +3 apparent oxidation state; and

Q is each independently selected from hydride, dialkylamide, halide, hydrocarbyl, alkoxide, halogen substituted hydrocarbyl, halogen substituted hydrocarbyloxy, and halogen substituted silyl hydrocarbyl (including perhalogenated hydrocarbyl-perhalogenated hydrocarbyloxy and perhalosilylhydrocarbyl), said Q having up to 20 carbon atoms, with the proviso that at most one of the Qs is a halide. Examples of suitable alkoxide Q groups are described in US 5,296,433, the disclosure of which is incorporated herein by reference.

In a more preferred embodiment, d is 1, that is, the counterion has a single negative charge and is A ^-1 , and the activating cocatalyst comprising boron which is particularly suitable for preparing the catalyst of the present invention can be represented by the following general formula:

(L ^* -H) ⁺ [BQ ₄ ] ^-

in:

L ^* as previously defined;

B is boron in apparent oxidation state 3; and

Q is a hydrocarbyl-, hydrocarbyloxy-, fluorohydrocarbyl-, fluorohydrocarbyloxy, or fluorosilylhydrocarbyl group having up to 20 non-hydrogen atoms, provided that at most one of Q is hydrocarbyl.

Q is most preferably each fluoroaryl, especially pentafluorophenyl.

Illustrative but non-limiting examples of ion-forming compounds including proton-donating cations that can be used as activating co-catalysts in the preparation of the catalysts of the present invention are

Trisubstituted ammonium salts, such as:

Trimethylammonium tetraphenylborate,

Methyl di(octadecyl)ammonium tetraphenylborate,

Triethylammonium tetraphenylborate,

Tripropylammonium tetraphenylborate,

Tri-n-butylammonium tetraphenylborate,

Methyl tetradecyl octadecyl ammonium tetraphenyl borate,

Tetraphenylboronic acid N,N-dimethylaniline salt,

N, N-diethylaniline tetraphenyl borate,

N, N-dimethyl (2,4,6-trimethylaniline) salt of tetraphenylboronic acid,

Trimethylammonium tetrakis(pentafluorophenyl)borate,

Triethylammonium tetrakis(pentafluorophenyl)borate,

Tripropylammonium tetrakis(pentafluorophenyl)borate,

Tri-n-butylammonium tetrakis(pentafluorophenyl)borate,

Methyltri-sec-butylammonium tetrakis(pentafluorophenyl)borate,

Tetrakis(pentafluorophenyl)boronic acid N,N-dimethylaniline salt,

Tetrakis(pentafluorophenyl)boronic acid N,N-diethylaniline salt,

Tetrakis(pentafluorophenyl) borate N,N-dimethyl(2,4,6-trimethylaniline) salt,

Trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

Triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

Tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

Tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

Tetrakis(2,3,4,6-tetrafluorophenyl) dimethyl tert-butylammonium borate,

Tetrakis(2,3,4,6-tetrafluorophenyl)boronic acid N,N-dimethylanilinium salt,

Tetrakis(2,3,4,6-tetrafluorophenyl)boronic acid N,N-diethylaniline salt and

Tetrakis(2,3,4,6-tetrafluorophenyl) borate N,N-dimethyl(2,4,6-trimethylaniline) salt;

Dialkylammonium salts such as di(isopropyl)ammonium tetrakis(pentafluorophenyl)borate and dicyclohexylammonium tetrakis(pentafluorophenyl)borate;

Trisubstituted phosphonium salts such as triphenylphosphonium tetrakis(pentafluorophenyl)borate, tris(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate and tris(2,6-bis(pentafluorophenyl)borate) methylphenyl) phosphonium.

Preference is given to long-chain alkyl mono- and disubstituted ammonium complexes, especially C ₁₄ -C ₂₀ alkyl ammonium complexes, especially methyl dioctadecyl ammonium tetrakis(pentafluorophenyl)borate, Methylditetradecylammonium tetrakis(pentafluorophenyl)borate.

A particularly preferred class of activating cocatalysts are tris(pentafluorophenyl)borane, tetrakis(pentafluorophenyl)boronic acid NR ₃ , NR ₄ aniline salts, wherein R ₃ and R ₄ are independently substituted or unsubstituted A saturated hydrocarbon group having 1 to 8 carbon atoms, (R ₁ R ₂ NHCH ₃ ) ⁺ (C ₆ H ₄ OH)B(C ₆ F ₅ ) ₃ ^- or (R ₁ R ₂ NHCH ₃ ) ⁺ B(C ₆ F ₅ ) ₄ ^- , wherein R ₁ and R ₂ are independently substituted or unsubstituted saturated hydrocarbon groups having 12 to 30 carbon atoms.

Another suitable ion-forming activating cocatalyst includes a salt of a cationic oxidizing agent with a non-coordinating compatible anion represented by the general formula:

(Ox ^e+ ) _d (A ^d- ) _e where:

Ox ^e+ is a cationic oxidant with charge e ⁺ ;

e is an integer from 1 to 3; and

A ^d- and d are as previously defined.

Examples of cationic oxidizing agents include: ferrocene cations, hydrocarbyl substituted ferrocene cations, Ag ⁺ or Pb ⁺² . Preferred embodiments of A ^d- are those anions defined above for activating cocatalysts containing Bronsted acids, in particular tetrakis(pentafluorophenyl)borate.

Another suitable ion-forming activating cocatalyst comprises a compound of the salt of a carbonium ion with a non-coordinating compatible anion represented by the general formula:

 ⁺ A ^-

in:

 ⁺ is a C _1-20 carbonium ion; and

A ^- as previously defined. The preferred  ⁺ is a trityl group, ie a tritylium ion.

Further suitable ion-forming activating cocatalysts include a compound of a salt of a silylium ion and a non-coordinating compatible anion represented by the general formula:

R ₃ Si(X′) _q ⁺ A ^-

in:

R is a C _1-10 hydrocarbon group, and X', q and A ^- are as defined above.

Preferred siliconium salt activating cocatalysts are trimethylsiliconium tetrakis(pentafluorophenyl)borate, triethylsiliconium tetrakis(pentafluorophenyl)borate, and ether substituted adducts thereof. Siliconium salts have generally been disclosed in the Journal of Organic Chemistry, Chemical Communications (J.Chem.Soc.Chem.Comm.). 1993, 383-384, and Lambert, J.B., et al., Organometallic Chemistry, 1994, 13, 2430 -2443 in. The above-mentioned silium salt is used as an activation co-catalyst in the catalyst of addition polymerization in the U.S. patent (applicant DavidNeithamer, David Devore, Robert LaPointe and Robert Mussell, filing date September 12, 1994).

Certain complexes of alcohols, thiols, silanols, and oximes with tris(pentafluorophenyl)borane are also effective catalyst activators and are useful in the present invention. These cocatalysts are disclosed in US 5,296,433, the disclosure of which is incorporated herein by reference.

Bulk electrolysis techniques involve the electrochemical oxidation of metal complexes under electrolytic conditions in the presence of a supporting electrolyte comprising a non-coordinating inert anion. In this technique, the solvents, supporting electrolytes, and electrolysis potentials used should substantially not form electrolysis by-products that would cause the metal complex to lose its catalytic activity during the reaction. More specifically, suitable solvents are substances that are inert liquids capable of dissolving the supporting electrolyte under electrolysis conditions (usually at a temperature of 0 to 100° C.). "Inert solvents" are those solvents which are not reduced or oxidized under the reaction conditions used in the electrolysis. In consideration of the desired electrolysis reaction, solvents and supporting electrolytes can generally be selected that are not affected by the potential used for the desired electrolysis. Preferred solvents include difluorobenzene (all isomers), dimethoxyethane (DME) and mixtures thereof.

Electrolysis can be performed in a standard electrolytic cell comprising an anode and a cathode (also known as working and counter electrodes, respectively). Suitable materials for constituting the electrolytic cell are glass, plastics, ceramics and glass-coated metals. The electrode is prepared from an inert conductive material, which refers to a conductive substance that is not affected by the reaction mixture or reaction conditions. Platinum or palladium are preferred inert conductive substances. Usually an ion permeable membrane such as a fine glass frit divides the electrolytic cell into separate compartments: a working electrode compartment and a counter electrode compartment. The working electrode is immersed in a reaction medium including the metal complex to be activated, solvent, supporting electrolyte, and any other substances necessary to regulate electrolysis or stabilize the resulting complex. The counter electrode is immersed in a mixture of solvent and supporting electrolyte. The required voltage can be determined by theoretical calculations or experimentally by scanning the cell with a reference electrode such as a silver electrode immersed in the cell's electrolyte. At the same time, the cell background current, ie the current in the absence of the desired electrolysis, is measured. Electrolysis is complete when the current drops from the desired value to the background current value. Complete conversion of the initial metal complex can be easily detected in this way.

Suitable supporting electrolytes are salts comprising a cation and a compatible non-coordinating anion ^A- . A preferred supporting electrolyte conforms to the general formula G ⁺ A ⁻ ; where:

G ⁺ is a cation inactive towards the starting and resulting complexes, and

A ^- as previously defined.

Examples of cations G ⁺ include tetrahydrocarbyl substituted ammonium or phosphonium cations having up to 40 non-hydrogen atoms. Preferred cations are the tetra-n-butylammonium- and tetraethylammonium cations.

During activation of the complexes of the invention by bulk electrolysis, the cations of the supporting electrolyte pass to the counter electrode and ^A- migrates to the working electrode to become an anion of the resulting oxidation product. The cations of the solvent or supporting electrolyte are reduced on the counter electrode in the same molar amount as the oxidized metal complex formed on the working electrode. Preferred supporting electrolytes are tetrahydrocarbyl ammonium salts of tetrakis(perfluoroaryl)boronic acid having 1 to 10 carbon atoms in each hydrocarbyl or perfluoroaryl group, especially tetrakis(pentafluorophenyl)boronic acid tetra-n-butyl ammonium salt.

A recently discovered electrochemical technique for generating activated cocatalysts is the electrolysis of disilanes in the presence of noncoordinating compatible anions. This technique is disclosed and claimed in more detail in the aforementioned US patent application entitled "Siliconium Cationic Polymerization Activators of Metallocene Complexes" (filed September 12, 1994).

The electrochemical activation techniques described above can also be used in combination with activating co-catalysts. A particularly preferred combination is a mixture of tri(hydrocarbyl)aluminum or tri(hydrocarbyl)borane with oligomeric or polymeric aluminoxane compounds having 1 to 4 carbon atoms in each hydrocarbyl group.

The catalyst/cocatalyst molar ratio used is in the range of 1:10,000 to 100:1, more preferably 1:5000 to 10:1, most preferably 1:1000 to 1:1. When the aluminoxane itself is used as an activating cocatalyst, its amount is usually at least 100 times (by mole) that of the metal complex. When tris(pentafluorophenyl)borane is used as an activating cocatalyst, its amount is generally 0.5:1 to 10:1, more preferably 1:1 to 6:1, most preferably 1:1 to 5:1. The remainder of the activating cocatalyst is generally used in approximately equal molar amounts to the metal complex.

The process of the invention can be used to polymerize single ethylenically unsaturated monomers or mixtures thereof having 2 to 20 carbon atoms. Preferred monomers include: monovinylidene aromatic monomers, especially styrene, 4-vinylcyclohexene, vinylcyclohexane, norbornadiene; _C2-20 aliphatic-olefins, especially Ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene ; C _4-40 dienes; and mixtures thereof. The most preferred monomers are ethylene, propylene, 1-butene, 1-hexene, 1-octene, and mixtures of ethylene, propylene and non-conjugated dienes, especially ethylidene norbornene.

Generally, polymerization can be carried out under Ziegler-Natta or Kaminsky-Sinn type polymerization conditions well known in the art, ie, temperature 0-250°C, preferably 30-200°C, and pressure from ambient pressure to 10,000 atmospheres. Suspension, solution, slurry, gas phase, bulk, solid state powder polymerization and other process conditions may be used as desired. When these catalysts are used in gas phase or slurry polymerization processes, supports, especially silica, alumina or polymeric (especially poly(tetrafluoroethylene) or polyolefin) supports can be used and are suitable. The preferred amount of support is such that the weight ratio of catalyst (on a metal basis) to support is 1:100,000 to 1:10, more preferably 1:50,000 to 1:20, most preferably 1:10,000 to 1:10 30. One such polymerization process involves combining one or more -olefins with a catalyst of the present invention in one or more continuous stirred tank or tubular reactors connected in series or in parallel, optionally in a solvent, or in Contacting is optionally carried out in a fluidized bed gas phase reactor in the absence of solvent, and the resulting polymer is recovered. Condensed monomer or solvent can be fed to the gas phase reactor as known in the art.

In most polymerization reactions, the molar ratio of catalyst to polymerizable compound used is from 10 ⁻¹² :1 to 10 ⁻¹ :1, more preferably from 10 ⁻⁹ :1 to 10 ⁻⁵ :1.

Suitable solvents for polymerization are inert liquids. Examples include: linear and branched hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane and mixtures thereof; cyclic or alicyclic hydrocarbons such as cyclohexane, cycloheptane, methane Cyclohexane, methylcycloheptane and their mixtures; perfluorocarbons, such as perfluoro C _4-10 alkanes, etc.; and aromatic hydrocarbons and alkyl-substituted aromatic compounds, such as benzene, toluene, xylene, ethylbenzene, etc. Suitable solvents also include liquid olefins that can be used as monomers or comonomers, including ethylene, propylene, butadiene, 1-butene, cyclopentene, 1-hexene, 1-heptene, 4-vinyl Cyclohexene, vinylcyclohexane, 3-methyl-1-pentene, 4-methyl-1-pentene, 1,4-hexadiene, 1-octene, 1-decene, styrene , divinylbenzene, allylbenzene, vinyltoluene (including individual isomers, or mixtures thereof) and the like. Mixtures of the aforementioned olefins are also suitable.

These catalyst systems may be used in separate reactors in series or in parallel with at least one auxiliary homogeneous or heterogeneous polymerization catalyst to produce polymer blends having the desired properties. An example of this method is disclosed in WO 94/005000 (identical to US Serial No. 07/904,770 and US Serial No. 08/10958, filed January 29, 1993), the disclosure of which is incorporated herein by reference.

Copolymers having high comonomer loadings and correspondingly low densities, but still having a low melt index, can be readily produced using the catalysts of the present invention. In other words, high molecular weight polymers can be obtained at high reactor temperatures using the catalysts of the present invention. The results obtained are particularly favorable because the molecular weight of alpha-olefin copolymers can be easily reduced by using hydrogen or similar chain transfer agents, whereas increasing the molecular weight of alpha-olefin copolymers can usually only be achieved by lowering the polymerization temperature of the reactor. Operating the reactor at low temperature will significantly increase the cost of operation disadvantageously, because heat must be removed from the reactor to maintain the low reaction temperature, and at the same time, the reactor fluid must be heated to evaporate the solvent. In addition, production efficiency is increased due to improved polymer solubility, reduced solution viscosity, and increased polymer concentration. Utilizing the catalysts of the present invention, -olefin homopolymers and copolymers having desired densities of 0.85 g/ ^cm3 to 0.96 g/ ^cm3 and melt flow rates of 0.001 to 10.0 dg/min are easily obtained in a high temperature process.

The catalyst system of the present invention is particularly advantageous for the production of ethylene homopolymers and ethylene/α-olefin copolymers having a high content of long chain branches. The use of the catalyst system of the present invention in a continuous polymerization process, especially a continuous solution polymerization process, allows for an increase in reactor temperature which favors the formation of vinyl-terminated polymer chains which can be incorporated into the growing polymer by This results in long chain branches. The use of the catalyst system of the present invention facilitates the economical production of ethylene/alpha-olefin copolymers having processability similar to low density polyethylene produced by the high pressure free radical process.

In another aspect of the present invention, the preferred method is an olefin high-temperature solution polymerization method: comprising combining one or more C _2-20 α-olefins with the catalyst system of the present invention under polymerization conditions at a temperature of about 100°C to about 250°C down contact. The temperature used in the process is more preferably from about 120°C to about 200°C, even more preferably from about 150°C to about 200°C.

The catalyst system of the present invention can be advantageously used in the production of diolefins with low "H" branching induced by the polymerization of ethylene alone or for the polymerization of dienes such as norbornadiene, 1,7-octadiene or 1,9-decadiene. Ethylene/alpha-olefin blends to produce olefin polymers with improved processability. The unique combination of high reactor temperature, high molecular weight (or low melt index) at high reactor temperature and high comonomer reactivity can facilitate the economical production of polymers with excellent physical properties and processability. These polymers preferably include _C3-20 alpha-olefins (including ethylene) and "H" branched comonomers. These polymers are preferably produced in a solution process, most preferably a continuous solution process. Furthermore, these polymers can be produced in gas phase or slurry processes.

As stated above, the catalyst system of the present invention is particularly suitable for the preparation of EP and EPDM copolymers in high yield and high production efficiency. The method used may be a solution or a slurry polymerization method, both of which are known in the art. Kaminsky, Journal of Polymer Science (J.Poly.Sci.), Vol. 23, pp. 2151-64 (1985), reported that a soluble bis(cyclopentadienyl)zirconium-aluminoxane catalyst system was used in Solution polymerized EP and EPDM elastomers. US 5,229,478 discloses a slurry polymerization process using a similar bis(cyclopentadienyl) zirconium based catalyst system.

Typically, elastomers such as EP and EPDM are produced under conditions that increase the activity of the diene monomer component. The reason for this is explained in the aforementioned '478 patent in the following manner (although applicable to the present invention). A major factor affecting production costs and the availability of EPDMs is the cost of the diene monomer. Dienes are more expensive monomeric species than ethylene or propylene. Furthermore, dienes are less reactive with known metallocene catalysts than ethylene and propylene. Therefore, in order to incorporate the required amount of diene to produce an EPDM with an acceptable fast cure rate, the concentration of diene monomer used (expressed as a percentage of the total monomer concentration present) must greatly exceed the concentration of diene monomer incorporated into the final EPDM product. Percentage of diene desired. Since most of the unreacted diene monomer must be recovered from the polymerization reactor recycle fluid, production costs are unnecessarily increased.

Another contributor to the cost of EPDM production is that the exposure of olefin polymerization catalysts to dienes, especially to the high concentrations of diene monomers required to incorporate the desired amount of dienes in the final EDPM product, often results in The catalytic rate or activity of the catalyst for the polymerization of ethylene and propylene monomers is reduced. As a result, lower feed amounts and longer reaction times are required compared to producing ethylene-propylene copolymer elastomers or other alpha-olefin copolymer elastomers.

The catalyst system of the present invention can advantageously increase the activity of diolefins, thereby producing EPDM polymers in high yields and production efficiencies. Furthermore, the catalyst system of the present invention enables the economical production of EPDM polymers with a diene content of up to 20% by weight or higher, which polymers have particularly suitable fast cure rates.

The non-conjugated diene monomer can be a linear, branched or cyclic diene having from about 6 to about 15 carbon atoms. Examples of suitable non-conjugated dienes are: linear acyclic dienes such as 1,4-hexadiene and 1,6-octadiene; branched acyclic dienes such as 5-methyl-1,4 -hexadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene and dihydromyrcene (myricene) and dihydroocimene ( mixed isomers of ocinene); monocyclic alicyclic diolefins such as 1,3-cyclopentadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, and 1,5-dodecadiene Dienes; and polyalicyclic fused and bridged cyclodienes, such as tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, bicyclo-(2,2,1)-hepta-2,5-diene ; alkenyl, alkylene, cycloalkenyl and cycloalkylene norbornene, such as 5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene, 5 -Isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylene-2-norbornene, 5-vinyl-2-norbornene alkenes and norbornadienes.

Among the dienes commonly used in the preparation of EPDM, particularly preferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene- 2-norbornene (VNB), 5-methylene-2-norbornene (MNB) and dicyclopentadiene (DCPD). Particularly preferred dienes are 5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).

Preferred EPDM elastomers may contain from about 20 to about 90 weight percent ethylene, more preferably from about 30 to about 85 weight percent ethylene, most preferably from about 35 to about 80 weight percent ethylene.

Alpha-olefins suitable for use with ethylene and dienes in the preparation of elastomers are preferably C _3-16 alpha-olefins. Illustrative non-limiting examples of these α-olefins are propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene and 1-dodecene. Typically from about 10 to about 80 wt%, more preferably from about 20 to about 65 wt%, of the alpha-olefin is added to the EPDM polymer. Typically from about 0.5 to about 20 wt%, more preferably from about 1 to about 15 wt%, most preferably from 3 to about 12 wt%, of the non-conjugated diene is added to the EPDM polymer. If necessary, more than one diene, such as HD and ENB, can be added simultaneously, and the total amount of diene added is within the above-mentioned range.

When the polymerization is carried out by the solution polymerization method, the catalyst system can be prepared as a homogeneous catalyst by adding the desired components to the solvent in which the polymerization will be carried out. Catalyst systems can also be prepared by absorbing the desired components on catalyst supports such as silica gel, alumina or other support substances and used as heterogeneous catalysts. When preparing catalyst systems in heterogeneous or supported form, silica is preferably used as support material. Inorganic support materials such as silica can be treated with aluminum alkyls or other chemical treating agents to reduce the surface hydroxyl content of the support. Heterogeneous forms of the catalyst system can be used in gas phase or slurry polymerizations. Due to practical constraints, slurry polymerization is carried out in a liquid diluent under conditions in which the polymer product is substantially insoluble. The diluent used in the slurry polymerization is preferably one or more hydrocarbons generally having less than 5 carbon atoms. If desired, saturated hydrocarbons such as ethane, propane or butane can be used in whole or in part as diluents. It is likewise possible to use alpha-olefin monomers or mixtures of different alpha-olefin monomers in whole or in part as diluents. The diluent most preferably comprises at least a major portion of the alpha-olefin monomer or monomer mixture to be polymerized.

The catalyst system of the present invention may comprise an aluminum organometallic component comprising aluminoxanes, aluminum alkyls or mixtures thereof. This component may be present in a non-activating amount and function primarily as a scavenger, or may interact with the cocatalyst component to enhance the activity of the catalyst component, or both.

It should be noted that suitable functional groups on the catalyst or co-catalyst of the catalyst system can be covalently or ionically bonded to the support material of the support component, which includes the support material, i.e., polymers, inorganic oxides, metal halides or mixture.

Preferred support materials for use in the present invention include porous silica, alumina, aluminosilicates, and mixtures thereof. The most preferred support material is silica. The carrier material can be particles, agglomerates, beads or any other physical form. Suitable carrier materials include, but are not limited to, commercially available under the designation SD3216.30, Davison Syloid 245, Davison 948 and Davison 952 from Grace Davison (a division of W.R. Grace & Co.), under the designation ES70 from Crossfield, and under the designation Aerosil 812 from Silica from Degussa AG; alumina available from Akzo Chemicals Inc. under the designation Ketzen Grade B.

Support materials suitable for the present invention preferably have a surface area of 10 to about 1000 m ² /g, more preferably of about 100 to 600 m ² /g (determined by nitrogen porosimetry using the BET method). The pore volume of the support (determined by nitrogen adsorption) is advantageously from 0.1 to 3 cm ³ /g, preferably from about 0.2 to 2 cm ³ /g. The average particle size depends on the method used, but is generally 0.5 to 500 μm, preferably 1 to 100 μm.

Silica and alumina are known to have small amounts of hydroxyl functionality themselves. When used as supports, these materials are preferably first subjected to thermal and/or chemical treatment to reduce their hydroxyl content. Usually the heat treatment is performed in an inert atmosphere or under reduced pressure at a temperature of 30°C to 1000°C for 10 minutes to 50 hours, preferably at a temperature of 250°C to 800°C for 5 hours or longer. Typically the chemical treatment involves contact with a Lewis acid alkylating agent such as a trihydrocarbyl aluminum compound, a trihydrocarbyl chlorosilane compound, a trihydrocarbyl alkoxysilane compound, or the like. Residual hydroxyl groups are then removed by chemical treatment.

The support can be functionalized with a silane or chlorosilane functionalizing agent to attach pendant silane-(Si-R)= or chlorosilane-(Si-Cl)= functional groups, where R is a C _1-10 hydrocarbon group. Suitable functionalizing agents are compounds which react with the surface hydroxyl groups of the support, or with the silicon or aluminum of the matrix. Examples of suitable functionalizing agents include phenylsilane, hexamethyldisilazane diphenylsilane, methylphenylsilane, dimethylsilane, diethylsilane, dichlorosilane and dichlorodimethylsilane . Techniques for forming these functionalized silica and alumina compounds are disclosed in US 3,687,920 and 3,878,368, the disclosures of which are incorporated herein by reference.

The support can also be treated with an aluminum compound selected from ^aluminoxanes or the general formula _AlRx1Ry2 , ^{wherein R1} is independently a hydride or R, ^R2 _is a hydride, R or OR, and x' is 2 or 3 , y' is 0 or 1, and the sum of x' and y' is 3. Examples of suitable R ^{and R} groups include methyl, methoxy, ethyl, ethoxy, propyl (all isomers), propoxy (all isomers), butyl (all isomers), isomers), butoxy (all isomers), phenyl, phenoxy, benzyl and benzyloxy. The aluminum component is preferably selected from aluminoxanes and tris(C _1-4 hydrocarbyl)aluminum compounds. The most preferred aluminum components are aluminoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum and mixtures thereof.

Aluminoxanes are oligomeric or polymeric aluminum oxy compounds containing alternating chains of aluminum and oxygen atoms, wherein the aluminum bears substituents, preferably alkyl groups. It is believed that the structures of aluminoxanes can be derived from the general formula (Al(R)-O) _m ' (for cyclic aluminoxanes) and the general formula R ₂ Al-O-(-Al(R)-O) _m '-AlR ₂ (for linear compounds) means wherein R is as defined above and m' is an integer from 1 to about 50, preferably at least about 4. Aluminoxanes are generally the reaction products of water and aluminum alkyls (which may contain, in addition to alkyl groups, halogen or alkoxy groups). Various alkylaluminum compounds such as trimethylaluminum and triisobutylaluminum react with water to form so-called modified or mixed aluminoxanes. A preferred aluminoxane is methylaluminoxane modified with a small amount of C _2-4 alkyl, especially isobutyl. Aluminoxanes generally contain small to relatively large amounts of starting alkylaluminum compounds.

A specific technique for the preparation of aluminoxanes by contacting an aluminum alkyl compound with an inorganic salt containing crystal water is disclosed in US 4,542,119. In a particularly preferred embodiment, the alkylaluminum compound is contacted with a renewable aluminum-containing material such as hydrated alumina, silica or other material. This process is disclosed in EP-A-338,044. It is thus possible by reacting hydrated alumina or silica substances (which have optionally been functionalized with silanes, siloxanes, alkoxysilanes or chlorosilanes) with tris(C _1-10 alkyl)aluminum compounds according to known techniques , aluminoxane can be added to the carrier. The aforementioned patents and publications, as well as the corresponding US application families, are incorporated by reference for the disclosure contained herein.

In order to also be filled with optional aluminoxane or trialkylaluminum, the treatment of the support material also involves combining the support material with an aluminoxane or a trialkylaluminum compound, especially a trialkylaluminum compound, before, after or simultaneously with the addition of the complex or activated catalyst. ethylaluminum or triisobutylaluminum contact. The mixture is also optionally heated under an inert atmosphere for a period of time at a temperature sufficient to immobilize the aluminoxane, trialkylaluminum compound, complex or catalyst system on the support. The treated aluminoxane or trialkylaluminum compound-containing support component may be subjected to one or more washes to remove aluminoxane or trialkylaluminum not immobilized on the support.

In addition to contacting the support with an aluminoxane, the in situ reaction can also be achieved by contacting unhydrolyzed silica or alumina or wet silica or alumina with a trialkylaluminum compound, optionally in the presence of an inert diluent. This produces aluminoxane. This method is well known in the art and is disclosed in EP-A-250,600, US-A-4,192,075 and US-A-5,008,228, the teachings of which patents and the corresponding US applications are incorporated herein by reference. Suitable aliphatic hydrocarbon diluents include pentane, isopentane, hexane, heptane, octane, isooctane, nonane, isononane, decane, cyclohexane, methylcyclohexane and both or mixtures of these diluents. Suitable aromatic diluents are benzene, toluene, xylene and other alkyl or halogen substituted aromatic compounds. The diluent is most preferably an aromatic hydrocarbon, especially toluene. After preparation as described above, the residual hydroxyl content is suitably reduced to less than 1.0 meq OH/g support using any of the techniques previously disclosed.

The cocatalysts of the present invention can also be combined with tri(hydrocarbyl)aluminum compounds, oligomeric or polymeric aluminoxane compounds having 1 to 10 carbon atoms in each hydrocarbyl group, 1 to 10 carbon atoms in each hydrocarbyl or hydrocarbyloxy group. A bis(hydrocarbyl)(hydrocarbyloxy)aluminum compound of carbon atoms, or a mixture of the above-mentioned compounds may be used in combination. The use of these aluminum compounds is beneficial because of their ability to scavenge impurities such as oxygen, water and aldehydes from the polymerization mixture. Preferred aluminum compounds include _C2-6 trialkylaluminum compounds, especially those wherein the alkyl group is ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl or isopentyl Those aluminum compounds, and methylaluminoxane, modified methylaluminoxane or diisobutylaluminoxane. The molar ratio of aluminum compound to metal complex is preferably 1:10,000 to 1000:1, more preferably 1:5000 to 100:1, most preferably 1:100 to 100:1.

In contrast, solution polymerization is carried out under conditions in which the diluent acts as a solvent for the corresponding reaction components, especially the EP or EPDM polymer. Preferred solvents include mineral oil and various hydrocarbons which are liquid at the reaction temperature. Illustrative examples of suitable solvents include: paraffins, such as pentane, isopentane, hexane, octane, and nonane; and mixtures of paraffins, including gasoline and Isopar E ^™ (available from Exxon Chemical Inc.); alkanes such as cyclopentane and cyclohexane; and aromatics such as benzene, toluene, xylene, ethylbenzene and diethylbenzene.

At all times, the components and recovered catalyst components must be protected from oxygen and moisture damage. Catalyst components must therefore be prepared and recovered in an atmosphere free of oxygen and moisture. Therefore, the reaction is preferably carried out under a dry inert gas such as nitrogen.

Ethylene is fed to the reactor in excess of the total vapor pressure of the alpha-olefin and diene to maintain the pressure differential. The ethylene content of the polymer is determined from the ratio of the ethylene differential pressure to the total reactor pressure. Polymerization is typically carried out at a differential ethylene pressure of from about 10 to about 1000 psi (70 to 7000 ka), most preferably from about 40 to about 400 psi (30 to 300 kPa). Polymerization is generally carried out at a temperature of from about 25 to about 200°C, preferably from 75 to 170°C, most preferably greater than 95 to 140°C.

Polymerization can be carried out batchwise or continuously. A continuous polymerization process is preferred, in which case catalyst, ethylene, alpha-olefin and optionally solvent and diene are continuously fed into the reaction zone and polymer product is continuously withdrawn therefrom. The term "continuous" or "continuously" as used herein means that the addition of reactants and withdrawal of product are intermittent at short intervals so that the process as a whole is continuous.

Without limiting the scope of the invention in any way, one way of carrying out the polymerization process is as follows: propylene monomer is fed continuously into a stirred tank reactor together with solvent, diene monomer and ethylene monomer. The reactor contains a liquid phase consisting essentially of ethylene, propylene and dienes and solvent or another diluent. If desired, small amounts of "H"-branching inducing dienes such as norbornadiene, 1,7-octadiene or 1,9-decadiene can also be added. Catalyst and cocatalyst are continuously fed into the liquid phase of the reactor. Reactor temperature and pressure can be controlled by adjusting the solvent/monomer ratio, catalyst addition rate, and by cooling or heating coils, jackets, or both. The rate of polymerization is controlled by the rate of catalyst addition. The ethylene content of the polymer product is determined by the ratio of ethylene to propylene in the reactor which is controlled by adjusting the relative feed rates of these components to the reactor. The molecular weight of the polymer product is optionally controlled by, for example, controlling other polymerization variables such as temperature, monomer concentration, or by hydrogen flow into the reactor as is known in the art. The reactor effluent is contacted with a catalyst deactivating agent such as water. The polymer solution is optionally heated and flashed off under reduced pressure to ethylene, propylene and residual solvent or diluent, and if necessary further devolatilized in a devolatilization extruder unit such as a devolatilizing extruder to recover the polymer product. In continuous polymerization processes, the average residence time of catalyst and polymer in the reactor is from about 5 minutes to 8 hours, preferably from 10 minutes to 6 hours.

In a preferred mode of operation, the polymerization is carried out in a solution polymerization system comprising two reactors connected in series or in parallel. A relatively high molecular weight product (Mw 300,00 to 600,000, more preferably 400,000 to 500,000) is formed in one reactor while a relatively low molecular weight product (Mw 50,000 to 300,000) is formed in the second reactor. The final product was a blend of the two reactor products, which were combined prior to devolatilization to obtain a homogeneous blend of the two polymer products. This dual reactor approach can produce products with improved properties. In a preferred embodiment, the reactors are connected in series, ie the discharge stream from the first reactor is fed to the second reactor and fresh monomer, solvent and hydrogen are fed to the second reactor. The reaction conditions are adjusted so that the weight ratio of the polymer produced in the first reactor to the polymer produced in the second reactor is 20:80 to 80:20. In addition, the temperature of the second reactor is controlled to produce low molecular weight products. This system advantageously produces EPDM products with a wide range of Mooney viscosities combined with excellent strength and processability. The Mooney viscosity (ASTM D 1646-94ML+4@125°C) of the resulting product is preferably adjusted to within the range of 1-200, preferably 5-150, most preferably 10-110.

The process according to the invention can be used advantageously, for example, for the gas-phase polymerization of olefins. Olefin gas phase polymerization method, especially the homopolymerization and copolymerization of ethylene and propylene, and the homopolymerization and copolymerization of ethylene and higher α-olefins such as 1-butene, 1-hexene, 4-methyl-1-pentene are the basic well known in the field. These processes are used industrially on a large scale for the production of high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE) and polypropylene.

The gas phase process used may be any gas phase process using a mechanically stirred bed or a gas phase fluidized bed as the polymerization reaction zone. Preferred is where the polymerization is carried out in a vertical cylindrical polymerization reactor comprising a fluidized bed of polymer particles supported or suspended on perforated plates, fluidization grids fluidized by fluidization gas.

The gas used for fluidization includes the monomers to be polymerized and also acts as a heat exchange medium for removing heat from the fluidized bed. Hot gases are withdrawn from the top of the reactor through a plateau (also known as a velocity drop zone, which is wider in diameter than the fluidized bed) where fine particles entrained in the gas stream have an opportunity to settle back into the bed. It may also be advantageous to use a cyclone to remove ultrafine particles from the hot gas stream. The gas is then recycled into the bed by means of a blower or compressor and one or more heat exchangers (to remove the heat of polymerization from the gas).

A preferred method of cooling the fluidized bed, in addition to the cooling provided by the cooled recycle gas, is to add a volatile liquid to the bed to provide evaporative cooling (commonly referred to as condensing mode operation). The volatile liquid used in this case may be a volatile inert liquid such as a saturated hydrocarbon having from about 3 to about 8, preferably 4 to 6 carbon atoms. Where the monomer or comonomer is itself a volatile liquid or can be condensed to provide such a liquid, it may be suitably added to the bed to provide an evaporative cooling effect. Examples of olefinic monomers which may be used in this manner are olefins containing from about 3 to about 8, preferably 3 to 6 carbon atoms. The volatile liquid evaporates in the heated fluidized bed to form a gas which is mixed with the fluidizing gas. If the volatile liquid is monomer or comonomer, some polymerization will take place in the bed. The evaporated liquid exits the reactor as part of the hot recycle gas and enters the compression/heat exchange unit of the hot recycle loop. The recirculated gas is cooled in a heat exchanger, and if the temperature of the cooled gas is below the dew point, liquid is precipitated from the gas. The liquid is suitably recirculated continuously into the fluidized bed. The precipitated liquid can be recycled into the bed as droplets in the recycle gas stream. Such methods are described, for example, in EP 89691, US 4,543,399, WO 94/25495 and US 5,352,749, which are hereby incorporated by reference. A particularly preferred method of recycling liquid into the bed is to separate the liquid from the recycle gas stream and reinject the liquid directly into the bed, preferably by generating fine droplets within the bed. This method is described in WO 94/28032 by BP Chemical. This method is incorporated herein by reference.

Polymerizations carried out in gas-phase fluidized beds are catalyzed by continuous or semi-continuous addition of catalysts. The catalyst may be supported on an inorganic or organic carrier as described above. The catalyst may also be subjected to a prepolymerization step, for example by polymerizing a small amount of monomer in a liquid inert diluent, to provide a catalyst composite comprising catalyst particles embedded in olefin polymerized particles.

The polymer is produced directly in a fluidized bed by catalytic copolymerization of monomer and one or more comonomers on fluidized particles of catalyst, supported catalyst or prepolymer within the bed. Using a preformed bed of polymer particles (preferably similar to the target polyolefin) and conditioning the reaction bed by drying with inert gas or nitrogen prior to addition of catalyst, monomer and any other gases required in the recycle gas, allows The polymerization reaction is initiated, wherein examples of such other gases are diluent gases, hydrogen chain transfer agents or condensable inert gases used when operating in gas phase condensation mode. The produced polymer is discharged continuously or intermittently from the fluidized bed, if desired.

A gas phase process suitable for the practice of the present invention is preferably a continuous process which provides for the continuous addition of reactants to and discharge of products from the reaction section of the reactor whereby the reaction section of the reactor reacts on a macroscopic scale Provide a steady state environment.

Typically, the fluidized bed of the gas phase process is operated at a temperature greater than 50°C, preferably from about 60°C to about 110°C, more preferably from about 70°C to about 110°C.

Typically the comonomer to monomer ratio used in the polymerization is about 0.5 or less depending on the desired density of the polymer being produced. When it is desired to produce a material having a density of about 0.91 to about 0.93, the comonomer to monomer ratio is below 0.2, preferably below 0.05, more preferably below 0.02, and may even be below 0.01. Typically the ratio of hydrogen to monomer is less than about 0.5, preferably less than 0.2, more preferably less than 0.05, even more preferably less than 0.02, and may even be less than 0.01.

The above ranges for process variables are suitable for the gas phase process of the present invention, and may be suitable for other processes in which the present invention may be practiced.

很多专利和专利申请描述了适用于本发明方法的气相聚合方法，它们特别为：US4,588,790、4,543,399、5,352,749、5,436,304、5,405,922、5,462,999、5,461,123、5,453,471、5,032,562、5,028,670、5,473,028、5,106,804，EP申请659,773 , 692,500, and PCT applications WO 94/29032, WO 94/25497, WO 94/25495, WO 94/28032, WO 95/13305, WO 94/26793, and WO 95/07942, all of which are incorporated herein by reference.

The catalysts in any of the preceding processes, whether supported or not, can be used to polymerize single acetylenically unsaturated monomers or mixtures thereof having from 2 to 100,000 carbon atoms. Preferred monomers include C _2-20 α-olefins, especially ethylene, propylene, isobutene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl - 1-pentene, 1-octene, 1-decene, long-chain macro-olefins and mixtures thereof. Other preferred monomers include styrene, C _1-4 alkyl substituted styrene, tetrafluoroethylene, vinylbenzocyclobutane, ethylidene norbornene, 1,4-hexadiene, 1,7- Octadiene, vinylcyclohexane, 4-vinylcyclohexene, divinylbenzene and their mixtures with ethylene. Long-chain macromolecular alpha-olefins are vinyl-terminated polymer residues formed in situ during continuous solution polymerization reactions. These long chain macromolecular units are readily polymerized into polymer products together with ethylene and other short chain olefinic monomers under suitable processing conditions to obtain a small amount of long chain branching in the resulting polymer.

These catalysts may also be used with at least one auxiliary homogeneous or heterogeneous polymerization catalyst in the same, or in separate reactors connected in series or in parallel, to produce polymer blends having the desired properties. An example of this method is disclosed in WO 94/00500 (identical to US Serial No. 07/904,770 and US Serial No. 08/10958, filed January 29, 1993), the disclosure of which is incorporated herein by reference.

For preferred polyolefin polymer compositions producible by the inventive polymerization process employing the inventive catalyst system, the ratio of long chain branches to short chain branches formed by the incorporation of one or more -olefin comonomers into the polymer backbone long. The empirical effect of the presence of long-chain branches in the copolymers of the invention is evidenced by an increase in rheological properties, which can be demonstrated by higher flow activation energies and larger _I21 / _I2 than expected from other structural properties of the composition show.

Furthermore, the highly preferred polyolefin copolymer compositions of the present invention have an anomalous molecular structure, ie a molecular weight maximum occurs at 50% by weight of the composition of the maximum comonomer percentage. Especially when the catalyst system of the present invention having a single metallocene complex is produced in a single reactor in a process for the polymerization of α-olefins with one or more olefinic comonomers, especially when the process is a continuous process, it is furthermore Preferred polyolefin copolymer compositions are polyolefin copolymer compositions having long chain branches along the polymer backbone. Measuring the relationship between comonomer content and logarithm value of molecular weight by GPC/FTIR

The relationship between comonomer content and molecular weight was determined by Fourier transform infrared spectroscopy combined with Waters 150°C gel permeation chromatography. The composition, calibration and operation of the system and data processing methods have been published (LJRos et al., "Characterization of Ethylene Copolymers by Coupled GPC/FTIR", "Copolymer Characterization", Rapra Technology, Chawbury UK, 1995, ISBN 1-85975- 048-96). To characterize the degree of comonomer concentration in the high molecular weight fraction of the polymer, GPC/FTIR was used to calculate a parameter _Cpf called the comonomer partition factor. Simultaneously _Mn and _Mw were calculated from the GPC data using standard techniques. Comonomer partition factor (GPC-FTIR)

其中ci为摩尔分数共聚单体含量，wi为由GPC/FTIR对平均分子量以上的n个FTIR数据点测定的归一化重量分数。c_j为摩尔分数共聚单体含量，wj为由GPC/FTIR对平均分子量以下的m个FTIR数据点测定的归一化重量分数。仅与摩尔分数共聚单体含量值有关的wi和wj用于计算C_pf。为准确计算，要求n和m大于或等于3。因在该数据中存在的不确定性，在计算中不包括相应于5，000以下的分子量级分的FTIR数据。The partition factor C _pf of the comonomer was calculated from the GPC/FTIR data. This factor characterizes the ratio of the average comonomer content of the higher molecular weight fraction to the average comonomer content of the lower molecular weight fraction. Higher and lower molecular weights are respectively defined by above or below the average molecular weight, ie the average molecular weight is divided into two parts of equal weight. C _pf is defined by the following equation:

where ci is the mole fraction comonomer content and wi is the normalized weight fraction determined by GPC/FTIR for n FTIR data points above the average molecular weight. _cj is the mole fraction comonomer content, wj is the normalized weight fraction determined by GPC/FTIR for m FTIR data points below the average molecular weight. Only wi and wj related to mole fraction comonomer content values were used to calculate _Cpf . For accurate calculation, n and m are required to be greater than or equal to 3. FTIR data corresponding to molecular weight fractions below 5,000 were not included in the calculations due to uncertainties in the data.

For the polyolefin copolymer composition of the present invention, _Cpf is suitably equal to or greater than 1.10, more suitably equal to or greater than 1.15, further more suitably equal to or greater than 1.20, preferably equal to or greater than 1.30, more preferably equal to or greater than 1.40, Even more preferably equal to or greater than 1.50, still more preferably equal to or greater than 1.60. ATREF-DV

ATREF-DV has been described in US 4,798,081 (herein incorporated by reference), and "Automatic Analytical Temperature Rise Elution Fractional Determination of Short Chain Branching Distribution of Ethylene Copolymers" (Auto-ATREF), Journal of Applied Polymer Science (J.of Appl Pol Sci): Applied Polymer Proceedings 45, 25-37 (1990). ATREF-DV is a dual detector analytical system capable of fractionating semi-crystalline polymers such as linear low density polyethylene (LLDPE) according to crystallization temperature and simultaneously detecting the molecular weight of these fractions. For fractionation, ATREF-DV is similar to the Temperature Rising Elution Fractionation (TREF) assay that has been published in the open literature for the past 15 years. The main difference is that this TREF (ATREF) analytical technique is performed on a very small scale and does not actually separate the fractions, but instead combines a typical liquid chromatography (LC)-mass detector, such as an infrared single-frequency The detector is used to quantify the crystallization distribution as a function of elution temperature. This distribution can be translated into various further defined ranges: eg short chain branch frequency, comonomer distribution or possibly density. Therefore, this transformed distribution can be explained in terms of certain structural variables, such as the comonomer content distribution. However, it is usually straightforward to use ATREF in a conventional manner for comparison of various LLDPEs within a defined range of elution temperatures.

To obtain ATREF-DV data, a commercially available viscometer, such as Viskotek ^(TM) , specially adapted for LC analysis, can be used in conjunction with an IR mass detector. Together, these two LC detectors can be used to calculate the intrinsic viscosity of the ATREF-DV eluted fraction. Appropriate Mark Houwink constants, corresponding intrinsic viscosities, and appropriate coefficients can then be used to estimate the viscosity-average molecular weight of a given component and thereby estimate the fraction concentration (dl/g) as it passes the detector. Thus, a typical ATREF-DV report will provide polymer weight fraction and viscosity average molecular weight as a function of elution temperature. M _pf is then calculated using the given equation. molecular weight partition factor

其中Mi为粘均分子量，wi为由ATREF-DV对平均洗脱温度以下的n个数据点测定的归一化重量分数。M_j为粘均分子量，wj由ATREF-DV对平均洗脱温度以上的m个数据点测定的归一化重量分数。仅与大于0的粘均分子量有关的那些重量分数wi或wj用于计算M_pf。为准确计算，要求n和m大于或等于3。The molecular weight partition factor M _pf was calculated from TREF/DV data. This factor characterizes the ratio of the average molecular weight of the high comonomer content component to the average molecular weight of the low comonomer content component. Higher and lower comonomer contents are defined by below or above the average elution temperature of the TREF concentration plot, respectively, i.e. the TREF data is divided into two parts of equal weight. M _pf is defined by the following equation:

where Mi is the viscosity average molecular weight and wi is the normalized weight fraction determined by ATREF-DV for n data points below the average elution temperature. _Mj is the viscosity average molecular weight, wj is the normalized weight fraction determined by ATREF-DV for m data points above the average elution temperature. Only those weight fractions wi or wj associated with a viscosity average molecular weight greater than 0 are used in the calculation of M _pf . For accurate calculation, n and m are required to be greater than or equal to 3.

For the polyolefin copolymer composition of the present invention, M _pf is suitably equal to or greater than 1.15, more suitably equal to or greater than 1.30, further more suitably equal to or greater than 1.40, preferably equal to or greater than 1.50, more preferably equal to or greater than 1.60, Even more preferably equal to or greater than 1.70.

Example

Those skilled in the art will understand that the invention disclosed herein may be practiced in the absence of any components not specifically disclosed. The following examples are provided to further illustrate the present invention without limiting the present invention. All parts and percentages are by weight unless otherwise indicated.

All experiments involving organometallic compounds were performed using dry-box techniques. Solvents (THF, hexane, toluene, diethyl ether) were purified by alumina and Q5 column. C ₆ D ₆ was dried with Na/K alloy and vacuum distilled before use. NMR spectra were performed on a Varian XL-300 (FT 300 MHz, ¹ H; 75 MHz, ¹³ C). ¹ H NMR and ¹³ C{ ¹ H} NMR spectra refer to trace solvent peaks and are reported in ppm relative to tetramethylsilane. All J values are given in Hz. Mass spectra (EI) were acquired at AutoSpecQFDP. 1-Indanone, n-BuLi, Me ₂ SiCl ₂ , NH ₂ -t-Bu, NEt ₃ and MeMgI were purchased from Aldrich Chemical Co., and all compounds were used as received.

N-(1H-2-indenyl)-N, N-dimethylamine (Scandinavian Chemical Acta 1973,27,4027), 1-(1H-2-indenyl)-pyrrolidine (S Scandinavian Chemical Journal, 1973, 27, 4027), 2-ethoxy-1H-indene (Journal of the American Chemical Society, 1954, 106, 14) and tert-butyl-(1H-2-indenyloxy) - Dimethylsilane (Organometallic Chemistry, 1996, 15, 2450) was prepared according to literature methods.

Preparation of N-(1H-2-indenyl)-N,N-dimethylamine, lithium salt (1). In a dry box, 11.93 g (75.92 mmol) of N-(1H-2-indenyl)-N,N-dimethylamine were dissolved in a mixture of 200 mL of ether and 100 mL of hexane. To this solution, 51.51 mL (82.42 mmol) of n-BuLi (1.6M) was added dropwise. After the addition of n-BuLi was complete, the solution was stirred overnight. The resulting off-white precipitate was collected by filtration, washed with 100 mL of ether and dried under reduced pressure to yield 10.22 g of product. Yield 83%.

Preparation of N2,N2-Dimethyl-1-(1-(tert-butylamino)-1,1-dimethylsilyl)-1H-2-indenamine, (2). A solution of N-(1H-2-indenyl)-N,N-dimethylamine, lithium salt (2.07 g, 12.53 mmol) in 40 mL THF was added to N-tert-butyl-N-( 1-chloro-1,1-dimethylsilyl)amine in 30 mL THF solution. The reaction mixture was stirred for 7 hours and the solvent was removed under vacuum. The product was extracted with 30 mL of hexane and the solution was filtered through a medium sized frit. The hexane was removed under reduced pressure to leave 3.48 g of the product as a white solid. Yield 96%.

¹ H(C ₆ D ₆ )δ-0.01(s, 3H), 0.11(s, 3H), 100(s, 1H), 1.09(s, 9H), 2.43(s, 6H), 3.40(s, 1H ), 5.63 (s, 1H), 7.08 (t, 1H, ³ J _HH =7.1Hz), 7.23-7.32 (m, 2H), 7.40 (d, 1H, ³ J _HH =7.4Hz).

¹³ C{ ¹ H}(C ₆ D ₆ )δ-0.75, 0.39, 34.08, 42.44, 45.23, 49.47, 102.42, 11.8.31, 120.46, 122.63, 125.49, 140.45, 146.08, 161.75

Preparation of N2,N2--methyl-1-(1-(tert-butylamino)-1,1,-dimethylsilyl)-1H-2-indenamine, dilithium salt (3). In a dry box, 3.48 g (12.06 mmol) of N2, N2-dimethyl-1-(1-(tert-butylamino)-1,1,-dimethylsilyl)-1H-2-indene The amine was dissolved in 80 mL of hexane. To this solution, 18.0 mL (28.8 mmol) of n-BuLi (1.6M) was added dropwise. After the addition of n-BuLi was complete, the solution was stirred overnight. The resulting precipitate was collected by filtration, washed with 50 mL of hexane and dried under reduced pressure to obtain 3.40 g of a white solid. Yield 94%.

Preparation of dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-dimethylamino- 1H-inden-1-yl)silaneammine(2-)-N)titanium, (4). (N2,N2,-dimethyl-1-(1-(tert-butylamino)-1,1,-dimethylsilyl)-1H-2-indenamine dissolved in 30mL THF, di Lithium salt (3.40 g, 11.3 mmol) was added dropwise to a suspension of TiCl ₃ (THF) ₃ (4.19 g, 11.3 mmol) in 60 mL THF over 2 minutes. After mixing for 1 hour, PbCl ₂ (2.04 g, 7.34 mmol) was added ) solid. The reaction mixture was stirred for an additional 1.5 hours. The solvent was removed under reduced pressure. The residue was extracted with 70 mL of toluene and filtered through a medium-sized frit. The toluene was removed under reduced pressure and the residue was washed with 50 mL of hexane Triturate. Filtrate and collect brown-red solid, wash (2 * 30mL) with hexane, then dry under reduced pressure, obtain 3.22g brown-red solid product.Yield 70%

¹ H(C ₆ D ₆ )δ0.48(s, 3H), 0.64(5, 3H), 1.28-1.5(br, 6H), 1.38(s, 9H), 3.19

(m, 2H), 3.58(m, 3H), 5.92(s, 1H), 6.98(t, 1H, ³ J _HH =7.5Hz), 7.09(t, 1H, ³ J _HH =

7.5Hz), 7.52 (d, 1H, ³ J _HH =8.5Hz), 7.63 (d, 1H, ³ J _HH =8.7Hz).

¹³ C{ ¹ H}(C ₆ D ₆ )δ1.35, 4.15, 24.35, 26.14, 32.88, 51.62, 61.46, 92.92,

111.79, 125.08, 128.67, 128.92, 135.42, 151.09.

Preparation of (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-dimethylamino-1H- Inden-1-yl)silaneamine (2-)-N)dimethyltitanium, (5). In a dry box, 0.60 g of dichloro (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)- 2-Dimethylamino-1H-inden-1-yl)silaneammine(2-)-N)titanium (1.48 mmol) was dissolved in 35 mL _Et2O . To this solution was added dropwise 1.00 mL (3.00 mmol) MeMgI (3.0 M) over 5 minutes with stirring. The color of the solution changed from dark brown to greenish yellow. After the MeMgI addition was complete, the solution was stirred for 60 minutes. _Et2O was removed under reduced pressure and the residue was extracted with hexane (2 x 20 mL), the solution was filtered and the filtrate was evaporated to dryness under reduced pressure to afford 0.29 g (53% yield) of a yellow-green solid.

¹ H(C ₆ D ₆ )δ0.01(s, 3H), 0.58(s, 3H), 0.63(s, 3H), 0.98(s, 3H), 1.52(s, 9H), 2.45(s, 6H ), 6.17(s, 1H), 6.88(t, 1H, ³ J _HH =7.6Hz), 7.12(t.1H, ³ J _HH =8.0Hz), 7.40(d, 1H, ³ J _HH =8.3Hz) , 7.50 (d, 1H, ³ J _HH =8.32Hz)

¹³ C{ ¹ H}(C ₆ D ₆ )δ5.55, 6.71, 34.65, 45.87, 51.00, 57.97, 58.29, 79.96, 95.64, 124.23, 124.96, 125.46, 126.95, 130.31, 131.87, 161.99

Preparation of 1-(1H-2-indenyl)pyrrolidine, lithium salt (6). In a dry box, 15.2 g (82.2 mmol) of 2-pyrrolidinyl-indene were dissolved in a mixture of 150 mL toluene and 200 mL diethyl ether. To this solution, 53.84 mL (86.16 mmol) of n-BuLi (1.6M) was added dropwise. After the addition of n-BuLi was complete, the solution was stirred overnight. The resulting off-white precipitate was collected by filtration, washed with 70 mL of hexane and dried under reduced pressure to yield 15.29 g of product. Yield 97.5%. Preparation of N-tert-butyl-N-(1,1-dimethyl-2-(2-tetrahydro-1H-1-pyrrolyl-1H-1-indenyl)silylamine, (7). A solution of 1-(1H-2-indenyl)pyrrolidine, lithium salt (5.0 g, 26.15 mmol) in 50 mL THF was added over 10-15 min to N-tert-butyl-N-(1-chloro-1, 1-Dimethylsilyl)amine (4.98 g, 30.07 mmol) in 50 mL THF. The reaction mixture was stirred overnight and the solvent was removed under vacuum. The product was extracted with 40 mL hexane, and the solution was subjected to medium A glass frit was filtered. The hexane was removed under reduced pressure, leaving 7.81 g of a white solid product. The yield was 95%.

¹ H(C ₆ D ₆ )δ-0.01(s, 3H), 0.07(s, 3H), 1.02(s, 1H), 1.10(s, 9H), 1.55(m, 4H), 2.77(m, 2H ), 3.06(m, 2H), 3.39(s, 1H), 5.59(s, 1H), 7.05(t, 1H, ³ J _HH =7.4Hz), 7.27(m, 2H), 7.40(d, 1H, ³ J _HH =7.4Hz).

¹³ C{ ¹ H}(C ₆ D ₆ )δ-0.38, 0.52, 25.21, 34.11, 46.35, 49.55, 50.43, 100.07, 117.89, 119.85, 122.46, 125.51, 139, 146.46, 159.04

Preparation of N-(1,1-dimethylethyl)-1,1-dimethyl-1-(2-(1-pyrrolidinyl)-1H-inden-1-yl)silylamine, dilithium salt (8). In a dry box, 4.56 g (14.51 mmol) of N-(1,1-dimethylethyl)-1,1-dimethyl-1-(2-(1-pyrrolidinyl)-1H-indene -1-yl)silylamine was dissolved in 80 mL of hexane. To this solution, 18.75 mL (30 mmol) of n-BuLi (1.6M) solution was added dropwise. After the addition of n-BuLi was complete, the solution was stirred overnight. The resulting precipitate was collected by filtration, washed with 50 mL of hexane and dried under reduced pressure to obtain 4.50 g of a white solid. Yield 95%.

Preparation of dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-pyrrolidine (yl)-1H-inden-1-yl)silaneammine(2-)-N)-titanium, (9). N-(1,1-dimethylethyl)-1,1-dimethyl-1-(2-(1-pyrrolidinyl)-1H-inden-1-yl) dissolved in 50 mL THF Silylamine, dilithium salt (4.50 g, 13.79 mmol) was added dropwise to a suspension of _TiCl3 (THF) ₃ (5.11 g, 13.79 mmol) in 60 mL THF over 2 minutes. After mixing for 1 hour, _PbCl2 (2.49 g, 8.96 mmol) was added as a solid. The reaction mixture was stirred for an additional 1 hour. The solvent was removed under reduced pressure. The residue was extracted with 70 mL of toluene and filtered through a medium sized frit. Toluene was removed under reduced pressure and the residue was triturated with 50 mL of hexane. The dark gray solid was collected by filtration, washed with hexane (2 x 30 mL), and dried under reduced pressure to yield 4.3 g of the product as a brownish red solid. Yield 72%.

¹ H(C ₆ D ₆ )δ0.51(s, 3H), 0.72(s, 3H), 1.29(m, 4H), 1.41(s, 9H), 2.99(m, 2H), 3.17(m, 2H ), 5.99(s, 1H), 6.92(t, 1H, ³ J _HH =7.8Hz), 7.12(t, 1H, ³ J _HH =7.7Hz), 7.32(d, 1H, ³ J _HH =8.2Hz) , 7.70(d, 1H, ³ J _HH =8.6Hz)

¹³ C{ ¹ H)(C ₆ D ₆ )δ6.20, 6.77, 25.68, 32.89, 52.81, 61.61, 84.45, 96.57, 125.77, 125.89, 126.79, 127.80, 133.47, 134.13, 160.00

Preparation of (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl) -1H-inden-1-yl)silaneamine(2-)-N)dimethyltitanium, (10). In a dry box, 0.60 g of dichloro (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)- 2-(1-Pyrrolidinyl)-1H-inden-1-yl)silaneammine(2-)-N)-titanium (1.39 mmol) was dissolved in 40 mL _Et2O . To this solution was added dropwise 0.975 mL (2.92 mmol) MeMgI (3.0 M) over 5 minutes with stirring. The color of the solution changed from dark brown to yellow-green. After the MeMgI addition was complete, the solution was stirred for 60 minutes. _Et2O was removed under reduced pressure and the residue was extracted with hexane (2x20 mL), the solution was filtered and the filtrate was evaporated to dryness under reduced pressure to afford 0.39 g (72% yield) of a yellow-orange solid.

¹ H(C ₆ D ₆ )δ0.02(s, 3H), 0.56(s, 3H), 0.68(s, 3H), 1.00(s, 3H), 1.41(m, 4H), 1.53(s, 9H ), 2.88(m, 2H), 3.05(m, 2H), 6.19(s, 1H), 6.89(t, 1H, ³ J _HH =7.7Hz), 7.14(t, 1H, ³ J _HH =8.5Hz) , 7.43(d, 1H, ³ J _HH =8.3Hz), 7.56(d, 1H, ³ J _HH =8.6Hz)

¹³ C{ ¹ H)(C ₆ D ₆ )δ6.33, 7.17, 25.05, 34.72, 50.69, 53.75, 57.80, 58.01, 78.90, 94.44, 123.96, 124.87, 125.29, 126.67, 130.16, 131.79, 158.86

Preparation of dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-pyrrolidine base)-1H-inden-1-yl)silaneammine(2-)-N)-zirconium. N-(1,1-dimethylethyl)-1,1-dimethyl-1-(2-(1-pyrrolidinyl)-1H-inden-1-yl)silylamine, dilithium salt (3.00 g, 9.60 mmol) of the solid was added to a slurry of _ZrCl4 (2.24 g, 9.60 mmol) in toluene (100 mL). The mixture was stirred overnight. After completion of the reaction, the mixture was filtered and volatile components were removed to obtain the desired golden microcrystalline solid (3.02 g, yield 68%).

¹ H NMR (C ₆ D ₆ ) δ0.54(s, 3H), 0.69(s, 3H), 1.3-1.5(m, 4H), 1.34(s, 9H), 3.0-3.1(m, 4H), 5.81(s, 1H), 6.98(t, 1H, ³ J _HH =8.16Hz), 7.10(t.1H, ³ J _HH =8.01), 7.32(d, 1H, ³ J _HH =8.25Hz), 7.70( d, 1H, ³ J _HH =8.49Hz)

¹³ C NMR (C ₆ D ₆ ): δ6.72, 7.09, 25.19, 33.35, 53.30, 56.04, 78.34, 90.38, 125.03, 126.1, 126.47, 128.50, 129.84, 131.71, 159.18.

Preparation of (N-(1,1-dimethylethyl)-1,1-dimethyl-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl)-1H -Inden-1-yl)silaneamine(2-)-N)zirconium dimethyl, (12). Dichloro N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(1-pyrrolidinyl )-1H-inden-1-yl)silaneammine (2-)-N)zirconium (0.86g, 1.81mmol) was stirred in diethyl ether (50mL) while slowly adding MeMgBr (3.98mmol, 1.33mL 3.0M diethyl ether solution). The mixture was then stirred overnight. After the reaction was complete, volatile materials were removed, and the residue was extracted with hexane and filtered. Removal of hexane gave the desired product as a light yellow solid (0.51 g, 65% yield).

¹ H NMR (C ₆ D ₆ ) δ-0.52(s, 3H), 0.36(s, 3H), 0.61(s, 3H), 0.71(s, 3H), 1.3-1.6(m, 4H), 1.40( s, 9H), 2.8-3.0(m, 2H), 3.0-3.2(m, 2H), 5.92(s, 1H), 6.96(t, 1H, ³ J _HH =8.10Hz), 7 10(t, 1H , ³ J _HH =7.98Hz), 7.36(d, 1H ³ J _HH =8.19Hz), 7.68(d, 1H, ³ J _HH =8.25Hz)

¹³ C NMR (C ₆ D ₆ ) δ6.90, 7.45, 24.72, 34.51, 35.13, 40.83, 53.86, 54.61, 75.97, 88.62, 124.05, 124.45, 125.02, 127.26, 131.44, 159.02.

Preparation of 2-ethoxy-1H-indene, lithium salt (13). In a dry box, 3.85 g (24.03 mmol) of 2-ethoxy-1H-indene were dissolved in 100 mL of hexane. To this solution, 19.5 mL (31.24 mmol) of n-BuLi (1.6M) was added dropwise. After the addition of n-BuLi was complete, the solution was stirred overnight. The resulting off-white precipitate was collected by filtration, washed with 50 mL of hexane and dried under reduced pressure to yield 3.91 g of product. Yield 98%.

Preparation of N-(1,1-dimethylethyl-1,1-dimethyl-1-(2-ethoxy-1H-inden-1-yl)silylamine, (14). The 2-ethyl A solution of oxy-1H-indene, lithium salt (3.91g, 23.5mmol) in 40mL of THF was added dropwise to the solution of N-tert-butyl-N-(1-chloro-1,1-dimethylsilyl)amine 80 mL THF solution. The reaction mixture was stirred overnight and the solvent was removed under vacuum. The product was extracted with 30 mL hexane, and the solution was filtered through a medium-sized frit. The hexane was removed under reduced pressure to give 6.45 g of yellow Oil product. The yield is 94.7%.

¹ H(C ₆ D ₆ )δ0.09(s, 3H), 0.14(s, 3H), 1.10(m, 1H), 1.09(s, 9H), 1.10(m, 3H), 3.39(s, 1H ), 3.62(m, 2H), 5.59(s, 1H), 7.09(t, 1H, ³ J _HH =7.3Hz), 7.27(m, 2H), 7.38(d, 1H, ³ J _HH =7.4Hz) .

¹³ C{ ¹ H}(C ₆ D ₆ )δ0.21, 0.41, 14.86, 34.08, 45.52, 49.61, 65.49, 98.11, 119.20, 121.75, 123.04, 125.51, 138.28, 144.80, 168.87,

Preparation of N-(1,1-Dimethylethyl)-1,1-dimethyl-1-(2-ethoxy-1H-inden-1-yl)silanamine, dilithium salt (15). In a dry box, 6.45 g (22.28 mmol) of N-(1,1-dimethylethyl-1,1-dimethyl-1-(2-ethoxy-1H-inden-1-yl) Silyl amine is combined with 120mL hexane.In this solution, 32mL (51.2mmol) n-BuLi (1.6M) is added dropwise.After n-BuLi has added, this solution is stirred overnight.The resulting precipitate is collected by filtration, washed with hexane ( 2×30 mL) and dried under reduced pressure to obtain 4.52 g off-white solid. Yield 67%.

Preparation of dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-ethoxy-1H -Inden-1-yl)silaneammine(2-)-N)-titanium, (16). N-(1,1-dimethylethyl)-1,1-dimethyl-1-(2-ethoxy-1H-inden-1-yl)silylamine dissolved in 40 mL THF, di Lithium salt (4.52 g, 15.0 mmol) was added dropwise to a suspension of _TiCl3 (THF) ₃ (5.56 g, 15.0 mmol) in 70 mL THF over 2 minutes. After mixing for 1 hour, _PbCl2 (2.71 g, 9.75 mmol) was added as a solid, and the reaction mixture was stirred for an additional 1 hour. The solvent was removed under reduced pressure. The residue was extracted with 70 mL of toluene and filtered through a medium sized frit. Toluene was removed under reduced pressure and the residue was triturated with 40 mL of hexane. The dark gray solid was collected by filtration, washed with hexanes (2 x 25 mL), and dried under reduced pressure to yield 2.65 g of product. Yield 44%.

¹ H(C ₆ D ₆ )δ0.58(s, 3H), 0.67(s, 3H), 1.02(t, 3H, ³ J _HH =6.8Hz), 1.38(s, 9H), 3.57(m, 1H ), 419(m, 1H), 6.03(s, 1H), 6.96(t, 1H, ³ J _HH =7.6Hz), 7.11(t, 1H, ³ J _HH =7.8Hz), 7.25(d, 1H, ³ J _HH =8.3Hz), 7.55(d, 1H, ³ J _HH =8.2Hz).

¹³ C{ ¹ H}(C ₆ D ₆ )δ 4.19, 4.89, 14.46, 32.63, 62.41, 66.73, 83.88, 98.92, 125.92, 127.25 127.36 128.58, 129.58 132.04 164.08 HRMS (EI, M ⁺ 05.0): Calculated 56 , found 405,0563.

Preparation of (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-ethoxy-1H-indene -1-yl)silaneammine(2-)-N)-dimethyl-titanium, (17). In a dry box, 0.40 g of dichloro (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)- 2-Ethoxy-1H-inden-1-yl)silaneammine(2-)-N)-titanium (0.98 mmol) was dissolved in 50 mL _Et2O . To this solution was added dropwise 0.69 mL (2.07 mmol) MeMgI (3.0 M) over 5 minutes with stirring. After the MeMgI addition was complete, the solution was stirred for 1 hour. _Et2O was removed under reduced pressure and the residue was extracted with hexane (3 x 35 mL), the solution was filtered and the filtrate was evaporated to dryness under reduced pressure to afford 0.28 g (78% yield) of a yellow solid.

¹ H(C ₆ D ₆ )δ-0.02(s, 3H), 0.59(s, 3H), 0.69(s, 3H), 0.89(s, 3H), 0.99(t, 3H, 3JH-H=6.9Hz )1.52(s, 9H), 3.59(m, 2H), 6.11(s, 1H), 6.92(t, 1H, ³ J _HH =7.6Hz), 7.14(t, 1H, ³ J _HH =8.5Hz), 7.41(d, 1H, ³ J _HH =8.3Hz), 7.46(d, 1H, ³ J _HH =8.5Hz),

¹³ C{ ¹ H}(C ₆ D ₆ )δ5.22, 5.78, 14.65, 34.60, 50.03, 57.52, 58.18, 65.69, 77.18, 93.53, 124.66, 125.04, 125.39, 127.32, 126.89, 163.47.

Preparation of tert-butyl(1H-2-indenyloxy)dimethylsilane, lithium salt (18). In a dry box, 5.0 g (20.2 mmol) of tert-butyl(1H-2-indenyloxy)dimethylsilane was dissolved in 200 mL of hexane. To this solution, 10.1 mL (20.2 mmol) of n-BuLi (2.0 M) was added dropwise. After the addition of n-BuLi was complete, the solution was stirred overnight. The resulting precipitate was collected by filtration, washed with hexane and dried under reduced pressure to obtain 4.20 g of product. Yield 82%.

Preparation of (2-((1-(tert-butyl)-1,1-dimethylsilyl)oxy)-1H-1-indenyl)(chloro)dimethylsilane, (19). A solution of tert-butyl(1H-2-indenyloxy)dimethylsilane, lithium salt (4.20 g, 16.64 mmol) in 25 mL of THF was added to a solution containing SiMe ₂ Cl ₂ (32.2 g, 249 mmol) over 30 minutes. 50mL THF solution. After the addition was complete, the reaction mixture was stirred overnight. The solvent was then removed under reduced pressure. The residue was extracted with hexane and the solution was filtered. The solvent was removed under reduced pressure to yield 5.44 g of product. Yield 96%.

¹ H(C ₆ D ₆ )δ0.03(s, 3H), 0.15(s, 3H), 1.52(m, 4H), 3.14(m, 4H), 3.43(s, 1H), 5.14(s, 1H ), 7.24(m, 2H), 7.23(m, 2H), 7.60(m, 2H).

¹³ C{ ¹ H}(C ₆ D ₆ )δ-0.75, 0.48, 25.51, 42.72, 50.52, 100.02, 103.77, 121.18, 121.29, 124.30, 124.70, 125.58, 141.29, 144.61, 150.50

Preparation of N-(tert-butyl)-N-(1-(2-((1-tert-butyl)-1,1-dimethylsilyl)oxy)-1H-1-indenyl)-1 , 1-dimethylsilyl)amine, (20). In a dry box, 5.44 g of (2-((1-(tert-butyl)-1,1-dimethylsilyl)oxy)-1H-1-indenyl)(chloro)dimethylsilane (15.92 mmol) combined with 150 mL of hexane. To this solution was added NEt ₃ (1.95 g, 19.25 mmol) and NH ₂ t-Bu (1.41 g, 19.25 mmol) and the solution was stirred overnight. The reaction mixture was filtered and the solvent was removed under reduced pressure to give 5.31 g of product .The yield is 88%.

¹ H(CDCl ₃ )δ0.11(s, 3H), 0.14(s, 3H), 0.38(s, 6H), 1.08(s, 9H), 1.25(s, 9H), 3.43(s, 1H), 5.88(s, 1H), 7.14(m, 1H), 7.23(m, 2H), 7.58(m, 1H)

Preparation of N-(tert-butyl)-N-(1-(2-((1-tert-butyl)-1,1-dimethylsilyl)oxy)-1H-1-indenyl)-1 , 1-dimethylsilyl)amine, dilithium salt (21). In a dry box, N-(tert-butyl)-N-(1-(2-((1-tert-butyl)-1,1-dimethylsilyl)oxy)-1H-1- Indenyl)-1,1-dimethylsilyl)amine (3.00 g, 8.63 mmol) was stirred in hexane (100 mL) while slowly adding n-BuLi (17.4 mmol, 8.70 mL 2.0M cyclohexane solution). The mixture was then stirred overnight, during which time a white solid precipitated. After the reaction, the desired product was collected by filtration, washed with hexane, and dried under vacuum to give the product as a white solid (1.58 g, yield 51%), which was not further purified or analyzed.

Preparation of dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(dimethyl- tert-Butylsilyloxy)-1H-inden-1-yl)silaneammine(2-)-N)-titanium, (22). (N-(1,1-Dimethylethyl)-1,1-dimethyl-1-(2-dimethyl-tert-butylsilyloxy-1H-inden-1-yl in 30 mLTHF ) silylamine, dilithium salt (1.58 g, 4.40 mmol) was added dropwise to a slurry of TiCl ₃ (THF) ₃ (1.63 g, 4.40 mmol) in THF (100 mL) at 0° C. The mixture was mixed at room temperature 2 hours, then PbCl ₂ (0.65g, 2.35mmol) solid was added to the mixture, and the reaction mixture was stirred for another 1 hour. After the reaction was finished, the volatiles were removed under reduced pressure, and the residue was extracted with toluene and filtered A red/orange residue was isolated after removal of the toluene, which was redissolved in hexane and filtered. The desired product was isolated as an orange solid after removal of the hexane (1.27 g, 62% yield).

¹ H NMR (CDCl ₃ ) δ0.34(s, 3H), 0.44(s, 3H), 0.75(s, 3H), 0.87(s, 3H),

0.98(s, 9H), 1.40(s, 9H), 6.56(s, 1H), 7.21(t, ³ J _HH =7.68Hz, 1H), 7.35(t, ³ J _HH =7.95Hz, 1H), 7.56 (d, ^3JHH =8.28Hz, 1H) _, 7.65 (d, ^3JHH =8.73Hz _, 1H).

¹³ C NMR (CDCl ₃ ) δ-3.77, -3.38, 4.40, 5.14, 18.80, 25.84, 32.39, 62.53, 86.17, 104.44, 125.48, 126.78, 126.94, 128.11, 129.10, 131.26, 161.07,

Preparation of (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(dimethyl-tert-butylmethyl Silyloxy)-1H-inden-1-yl)silaneammine(2-)-N)-di-methyl-titanium, (23). Dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(dimethyl- tert-Butylsilyloxy)-1H-inden-1-yl)silaneammine(2-)-N)-titanium (0.35g, 0.74mmol) was stirred in diethyl ether (75mL) while slowly adding MeMgBr (1.50mmol , 0.50mL 3.0M ether solution). The mixture was then stirred for 2 hours. After the reaction was complete, volatile components were removed, and the residue was extracted with hexane and filtered. The desired product was isolated as a yellow oil (0.21 g, 65% yield) after removal of the hexane.

¹ H NMR (C ₆ D ₆ ) δ0.33(s, 3H), 0.21(s, 3H), 0.25(s, 3H), 0.65(s, 3H), 0.73(s, 3H), 0.99(s, 9H), 1.12(s, 3H), 1.59(s, 9H), 6.55(s, 1H), 6.94(t, ³ J _{H- H} =7.8Hz, 1H), 7.19(t, ³ J _HH =7.4Hz , 1H), 7.47(d, ³ J _HH =8.3Hz, 1H), 7.53(d, ³ J _HH =8.5Hz, 1H)

¹³ C NMR (C ₆ D ₆ ) δ-3.61, -3.48, 5.62, 5.97, 18.84, 25.15, 34.60, 52.13, 57.79, 58.25, 80.38, 100.38, 124.70, 125.13, 125.56, 127.26, 128.56, 159.8. The polymerization data for the catalyst systems of the inventive metal complexes are given in the table below.

aggregated data Compound name ^a Density ^b MI ^c Efficiency ^d [N-(1,1-dimethylethyl)-1,1-dimethyl-1-[(1,2,3,4,5-η)-2,3,4,5-tetramethyl yl-2,4-cyclopentadien-1-yl]silylamino(2-)-N]dimethyltitanium 0.895 5 946,000 (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-(dimethyl tert-butylsilyloxy Base)-1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium 0.884 3.56 2,351,000 (N-(1,1-dimethylethyl)-1,1 dimethyl-1-((1,2,3,3a,7a-η)-2-ethoxy-1H-indene-1 -yl)silane ammine (2-)-N)dimethyltitanium 0.894 0.74 162,000 (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-dimethylamino-1H-indene -1-yl)-silaneammine (2-)-N)dimethyltitanium 0.913 0.63 271,000 a) cocatalyst is B(G ₆ F ₅ ) ₃ b) g/cm ³ c) melt index (g/10min) d) g polymer/gTi

Dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-dimethylamino-1H Data collection for X-ray structure determination of -inden-1-yl)silaneammine(2-)-N)titanium

A dark purple massive crystal with dimensions 0.21 x 0.17 x 0.06 mm was immersed in oil (Paratone N. Exxon) and attached to a thin glass fiber. The crystal was transferred into a Siemens SMART PLATFORM diffractometer equipped with a graphite monochromatic crystal, a MoK radiation source (λ = 0.71073 A), a CCD (charge coupled device) and an area detector held 5.078 cm from the crystal. Crystals were kept under a stream of cold nitrogen (-100°C) during data collection. Three groups of 20 frames each covering three vertical sectors of space were collected using the ω-scan method with a 10-second exposure time. These frames were integrated, followed by determination of reflectance indices and least squares calibration, resulting in crystal orientation matrices and monoclinic lattices.

The data collection was set up to cover a total of 1631 frames of more than one full hemisphere of data in four different collections, the frame scan parameters are listed in the table below. Times 2θ ω                         Scan Scan   Frame Exposure

Axis width (°) (#) Time (second) 1-29-26.00 0.00 54.68 2 -0.3 626 302 -21.00 90.00 54.68 2 -0.3 455 303-23.00 180.00 54.68 2-0.3 29-29-23.00 45.00 54.68 2 -0.3 250 305 -29 -26.00 0.00 54.68 2 -0.3 50 30

The last time (#5) is to re-measure the measurement values of the first 50 frames from the first time. The purpose of this is to check the stability of the crystal and diffractometer and to calibrate for crystal attenuation.

The diffractometer setup included a 0.8 mm collimator providing an X-ray beam of 0.8 mm diameter. The power of the ray generator is set to 50KV and 35mA. The program SMART ¹ was used for diffractometer control, frame scanning, calibration index, orientation matrix calculation, least squares calibration of unit cell parameters, crystal plane measurements and actual data collection. Program ASTRO ¹ was used to set the data collection strategy. data processing

All 1381 crystal raw data frames were read by the program SAINT ¹ and integrated with a 3D section algorithm. The obtained data were converted to obtain the hkd reflectance index and its intensity, and the standard deviation was estimated. Calibration for Lorentz and polarization effects was performed on these data. A total of 7842 reflections representing 2.55 to 1.70 redundancy were collected with _Rsym values of 2.9% (at the smallest 2Θ reflector) to 3.1% (at the largest 2Θ reflector (55°)). Perform crystal attenuation calibration with values below 1%. The parameters of the unit cell are precisely calibrated by performing least squares processing on the set 5415 reflection angles. The unit cell parameters are:

a=8.3173(3) a=91.324(1)°

b=9.1847(3) b=91.541(1)°

c=13.2048(5)  g=103.384(1)°

Ⅴ=980.54(6)3

Absorption calibration was performed according to BLessing ³ with the program SADBS ² . The absorption coefficient is 0.77 mm ^-1 , and the minimum and maximum transmission are 0.812 and 0.962, respectively.

Data processing was carried out with the program XPREP ¹ . The space group was determined to be P1(#2) (based on systematic absences). XPREP provides the following crystal parameters: 4362 unique reflections with indices -11≤h≤10, -8≤k≤12, -17≤1≤18 (R _int =1.94%).

Structure Interpretation and Calibration

Structures were obtained via SHELXTL5 ⁴ , from which the positions of all non-hydrogen atoms were obtained. Also in SHELXTL5 the full matrix least squares calibration was used to accurately determine the structure. Non-hydrogen atoms are accurately determined with anisotropic thermal parameters, and all hydrogen atoms are located by Difference Fourier plots and calibrated without any constraints. In the last calibration, using 3639 observed reflections with I > 2s(I), the resulting R ₁ , wR ₂ and S (goodness of fit) were 2.93%, 7.40% and 1.061, respectively. A secondary extinction calibration was performed with x=0.0025(12). The maximum and minimum residual electron density peaks in the Difference Fourier plot are 0.376 and -0.369, respectively. Calibrate with ^F2 instead of F value. The _R1 value was calculated to provide a reference to the conventional R value (but its function was not minimized). Also, wR ₂ rather than R ₁ is the function to be minimized. Structure Interpretation and Calibration

Structures were obtained via SHELXTL5, from which the positions of all non-hydrogen atoms were obtained. Also in SHELXTL5 the full matrix least squares calibration was used to accurately determine the structure. Non-hydrogen atoms are accurately determined with anisotropic thermal parameters, and all hydrogen atoms are located by Difference Fourier plots and calibrated without any constraints. In the last calibration, using 4838 observed reflections with I>2σ(I), 432 parameters were calibrated, resulting in R ₁ , wR ₂ and S (goodness of fit) of 3.13%, 7.17% and 1.023. A secondary extinction calibration was performed with x=0.0018(7). The maximum and minimum residual electron density peaks in the Difference Fourier plot are 0.324 and -0.368, respectively. Calibrate with ^F2 instead of F value. The _R1 value was calculated to provide a reference to the conventional R value (but its function was not minimized). Also, wR ₂ rather than R ₁ is the function to be minimized.

Linear absorption coefficient, atomic scattering factor and irregular dispersion calibration are given in International Tables for X-ray Crystallography (1974), Vol. IV, p. 55 (Birmingham: Kynoch Press. (currently distributed Quotient: Numerical calculations in D. Reidel, Dordrecht.)).

Figure 1 gives dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-dimethyl Crystal structure of amino-1H-inden-1-yl)silaneammine(2-)-N)titanium.

Correlation functions used for the above structure determination are given below. $R_1=\hat{A}\left(\right|\left|\mathrm{Fo}\right|-\left|\mathrm{Fc}\right|\left|\right)/\hat{A}\left|\mathrm{Fo}\right|$ ${\mathrm{wxya}}_2=\left[\hat{A}{({\mathrm{Fo}}^2-{\mathrm{Fc}}^2)}^2\right]/\hat{A}\left[w{\left({\mathrm{Fo}}^2\right)}^2\right]{]}^{1/2}$ $R_{\mathrm{int}.}=\hat{A}|{\mathrm{Fo}}^2-{\mathrm{Fo}}^2{\left(\mathrm{mean}\right)|}^2/\hat{A}[{\mathrm{Fo}}^2]$ $S=\left[\hat{A}\right[w{({\mathrm{Fo}}^2-{\mathrm{Fc}}^2)}^2]/{(\mathrm{no}-p)]}^{1/2}$ where n is the number of reflections and p is the total number of parameters calibrated. w=1/[s ² (Fo ² )+(0.0370 ^* p) ² +0.31 ^* p], p=[max(Fo ² , 0)+2 ^* Fc ² ]/3

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-ethoxy-1H-indene- Data collection for X-ray structure determination of 1-yl)silaneammine (2-)-N)dimethyltitanium

A flat crystalline _crystal of transparent red _{ONSiTiCl2C17H25} measuring about _0.4x0.2x0.06 mm was immersed in oil (Paratone N. Exxon) and attached to thin glass fibers. All measurements were performed on an Enraf-Nonius CAD4 diffractometer by graphite monochromatic Mo-Kα radiation.

The unit cell constants and orientation matrices used for data analysis (obtained by least squares using carefully selected 25 angles in the central reflection range 18.2 < 2θ < 23.6°) fit a C-central monoclinic unit cell with the following dimensions:

a=28.874(9)

b=9.924(3) β=121.99(2)°

c=16.294(3)

V=3959(2)3

For Z=8 and FW=406.28, the calculated density is 1.36 g/cm ³ . Based on systematicabsences:

hkl: h+k≠2n

hol: l≠2n Packing status, statistical analysis of intensity distribution, ie successful interpretation and calibration of structure, space group determined: C2/c (#15).

Data were collected at a temperature of -120±1°C using the omega-theta scanning technique to a maximum 2Θ value of 49.9°. The ω-scans of multiple strong reflections taken before data collection had an average width at half maximum of 0.25° and an off angle of 2.8°. Scanning (1.00+0.35 tan θ) was performed at variable speed 3.0-16.0°/min (ω). A moving counter background measurement of the moving crystal is made by scanning an additional 25% above or below the scanning range. The counter hole consists of a variable horizontal slit of width 2.0 to 2.5mm and a vertical slit set at 2.0mm. The diameter of the incident beam collimator is 0.7 mm, and the distance between the crystal and the detector is 21 cm. For strong reflections, an attenuator is automatically inserted in front of the detector. data restoration

Of the 3786 reflections collected, 3705 were unique (R _int =0.041). Three representative reflection intensities were measured after X-ray exposure every 90 minutes. Attenuation correction not performed. The linear absorption coefficient μ of Mo-Kα radiation is 7.7 cm ^-1 . Perform analytical absorbance correction. A scattering factor of 0.85 to 0.95 was obtained. Data were corrected for Lorentz and polarization effects. A secondary extinction correction was performed (coefficient = 1.34465e-08). Structure Interpretation and Calibration

The structure was interpreted by the direct method (SHELXS86: Sheldrick, GM (1985), "Crystallographic Computing" a (eds. GM Sheldrick, C. Kruger and R. Goddard, Oxford University Press, pp. 175-189) and using the Fourier technique ( DIRDIF94: Beurskens, PT; Admiraal, G., Beurskens, G.; Bosman, WP; de Gelder, R.; Israel, R. and Smits, JMM (1994). DIRDIF-94 program system, Technical Report of the CrystallographyLaboratory, University of Nijmegan, The Netherlands). Anisotropic calibration was performed for non-hydrogen atoms. Hydrogen atoms were included at ideal locations but not calibrated. Last full-matrix least-squares calibration ^a based on 2223 observed reflections (I > 3.00 σ(I)) and 209 variable parameters, and used for weighting and weighting convention factors for convergence (the maximum parameter displacement is 0.01 times esd):

R=∑||Fo|-|Fc||/∑|Fo|=0.040 $R_w=\sqrt{{\mathrm{\&Sigma;w}\left(\right|\mathrm{Fo}|-|\mathrm{Fc}\left|\right)}^2/{\mathrm{\&Sigma;wFo}}^2)}=0.033$

The observed standard deviation of the unit weight ^b was 1.47. The weighting is based on count statistics. Plots of ∑w(|Fo|-|Fc|) ² versus |Fo|, reflection magnitude, sin θ/λ, and various exponents in the data collection showed no unusual trends. The maximum and minimum peaks on the final Fourier diagram correspond to 0.37 and -0.35e ^- /A ³ , respectively.

Neutral atom scattering factors were taken from Cromer and Waber (Cromer, D.T. & Waber, J.T., "International Tables for X-ray Crystallography", Vol. IV, The Kynoch Press, Birmingham, England, Table 2.2A (1974)). The anomalous dispersion effect is included in Fcalc (Ibers, J.A. & Hamilton, W.C., Acta Crystallogr., 17, 781 (1964)); the values Δf and Δf" are those of Creagh and McAuley (Creagh, D.C. & McAuley, W.J. , "International Tables for X-ray Crystallography", Vol. C., (ed. by A.J.C. Wilson), Kluwer College Press, Boston, Tables 4.2.6.8, pp. 219-222 (1992). The mass attenuation coefficient is Creagh and Hubbel's Those (Creagh, D.C. & Hubbel, J.H., "International Tables for X-ray Crystallography", Vol. C. (ed. A.J.C. Wilson), Kluwer College Press, Boston, Tables 4.2.4.3, pp. 200-206 (1992)) All calculations were performed with the crystallographic software package teXsan from the Molecular Structure Corporation (teXsan: Crystal Structure Analysis Software Package (1985 & 1992)). (a) Least squares method:

Function minimization: ∑w(|Fo|-|Fc|) ² where $w=\frac{1}{{\mathrm{\&sigma;}}^2\left(\mathrm{Fo}\right)}=\frac{{4\mathrm{Fo}}^2}{{\mathrm{\&sigma;}}^2\left({\mathrm{Fo}}^2\right)}$ ${\mathrm{\&sigma;}}^2\left({\mathrm{Fo}}^2\right)=\frac{{\mathrm{the\; s}}^2\left({C+R}^{2}B\right)+{\left(f^2\right)}^2}{{\mathrm{LP}}^2}$

s-scan rate

C = total integral peak

R - ratio of scan time to background count time

B - total background count

Lp=Lorentz-polarization factor

p=p-factor. (b) Observed standard deviation of unit weight: $\sqrt{\mathrm{\&Sigma;w}{\left(\right|\mathrm{Fo}|-|\mathrm{Fc}\left|\right)}^2/(\mathrm{no}-\mathrm{Nv})}$

where No=number of observations

Nv = number of variables.

Figure 2 gives (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-2-ethoxy- Crystal structure of 1H-inden-1-yl)silaneammine (2-)-N)dimethyltitanium.

Claims (64)

1. metal complexes corresponding to following general formula:

Wherein M is the metal that is selected from the periodic table of elements the 3rd to 13 family, group of the lanthanides or actinium series, its apparent oxidation state is+2 ,+3 or+4, this metal and a cyclopentadienyl (Cp) π-bonding, described cyclopentadienyl is for having 5 substituting group (R ^A) _j-T, R ^B, R ^C, R ^DWith ring-type delocalization π-ligands bound thereto group of Z, wherein j is 0,1 or 2; R ^A, R ^B, R ^C, R ^DBe the R group; Wherein

T is for Cp ring, when j is 1 or 2 and and R ^AThe heteroatoms of covalent bonding, when j was 0, T was F, Cl, Br or I; When j was 1, T was O or S, perhaps was N or P and R ^AAnd has a pair of key between the T; When j was 2, T was N or P; Wherein

R ^AIndependently of each other for hydrogen or for having the group of 1 to 80 non-hydrogen atom, described group is alkyl, silicon alkyl alkyl, halogen substituted hydrocarbon radical,-oxyl substituted hydrocarbon radical, hydrocarbon amino-substituted hydrocarbyl, silicon alkyl alkyl alkyl, amino, the-oxyl of alkyl amino, two (alkyl), each R ^ARandomly can be replaced by one or more substituting groups, described substituting group is amino for-oxyl, silicon alkyl alcoxyl base, silicon alkyl alkyl amino, two (silicon alkyl alkyl) with 1 to 20 non-hydrogen atom independently of each other, alkyl is amino, two (alkyl) amino, two (alkyl) phosphino-, sulfenyl, alkyl, halogen substituted hydrocarbon radical,-oxyl substituted hydrocarbon radical, hydrocarbon amino-substituted hydrocarbyl, silicon alkyl alkyl or silicon alkyl alkyl alkyl, or has the no interaction group of 1 to 20 non-hydrogen atom; Each R ^B, R ^CAnd R ^DBe hydrogen, or have the group of 1 to 80 non-hydrogen atom that described group is alkyl, halogen substituted hydrocarbon radical,-oxyl substituted hydrocarbon radical, hydrocarbon amino-substituted hydrocarbyl, silicon alkyl alkyl, silicon alkyl alkyl alkyl, each R ^B, R ^CAnd R ^DRandomly can be replaced by one or more substituting groups, described substituting group is amino for-oxyl, silicon alkyl alcoxyl base, silicon alkyl alkyl amino, two (silicon alkyl alkyl) with 1 to 20 non-hydrogen atom independently of each other, alkyl is amino, two (alkyl) amino, two (alkyl) phosphino-, alkyl sulfide, alkyl, halogen substituted hydrocarbon radical,-oxyl substituted hydrocarbon radical, hydrocarbon amino-substituted hydrocarbyl, silicon alkyl alkyl or silicon alkyl alkyl alkyl, or has the no interaction group of 1 to 20 non-hydrogen atom; Or R randomly ^A, R ^B, R ^CAnd R ^DIn two or more covalent bondings mutually form and have one or more condensed ring or the member ring systems of 1 to 80 non-hydrogen atom for each R group, these one or more condensed ring or member ring systems are unsubstituted or are replaced by one or more substituting groups, described substituting group is independently of each other for having the-oxyl of 1 to 20 non-hydrogen atom, silicon alkyl alcoxyl base, silicon alkyl alkyl amino, two (silicon alkyl alkyl) amino, alkyl amino, two (alkyl) amino, two (alkyl) phosphino-, alkyl sulfide, alkyl, the halogen substituted hydrocarbon radical, the-oxyl substituted hydrocarbon radical, the hydrocarbon amino-substituted hydrocarbyl, silicon alkyl alkyl or silicon alkyl alkyl alkyl, or have the no interaction group of 1 to 20 non-hydrogen atom;

Z is the divalent moiety by σ key and Cp and M bonding, and wherein Z comprises the element of boron or the periodic table of elements the 14th family, also comprises nitrogen, phosphorus, sulphur or oxygen;

X has the negatively charged ion or the two anion ligand groups of 60 atoms at the most, does not comprise ring-type delocalization π-ligands bound thereto group class part;

X ' is independently of each other for having the neutral Lewis base coordination compound of 20 atoms at the most;

P is 0,1 or 2, and p lacks 2 than the apparent oxidation state of M when X is anion ligand; When X was two anion ligands, p was 1; With

Q is 0,1 or 2.

2. the metal complexes of claim 1, corresponding to following general formula:

R wherein ^W, R ^X, R ^YAnd R ^ZBe the R group, each group is hydrogen or alkyl, halogen substituted hydrocarbon radical,-oxyl substituted hydrocarbon radical, hydrocarbon amino-substituted hydrocarbyl, silicon alkyl alkyl, the silicon alkyl alkyl alkyl with 1 to 80 non-hydrogen atom independently, each R ^W, R ^X, R ^YAnd R ^ZRandomly can be replaced by one or more substituting groups, described substituting group is amino for-oxyl, silicon alkyl alcoxyl base, silicon alkyl alkyl amino, two (silicon alkyl alkyl) with 1 to 20 non-hydrogen atom independently of one another, alkyl is amino, two (alkyl) amino, two (alkyl) phosphino-, alkyl sulfide, alkyl, halogen substituted hydrocarbon radical,-oxyl substituted hydrocarbon radical, hydrocarbon amino-substituted hydrocarbyl, silicon alkyl alkyl or silicon alkyl alkyl alkyl, or has the non-interfering group replacement of 1 to 20 carbon atom; Or R ^W, R ^X, R ^Y, R ^Z, R ^AAnd R ^BIn two or more randomly mutually covalent bonding form one or more condensed ring or the member ring systems that each R group has 1 to 80 non-hydrogen atom, described one or more condensed ring or member ring systems are unsubstituted or by one or more-oxyls with 1 to 20 non-hydrogen atom, silicon alkyl alcoxyl base, silicon alkyl alkyl amino, two (silicon alkyl alkyl) amino, alkyl amino, two (alkyl) amino, two (alkyl) phosphino-, alkyl sulfide, alkyl, the halogen substituted hydrocarbon radical, the-oxyl substituted hydrocarbon radical, the hydrocarbon amino-substituted hydrocarbyl, silicon alkyl alkyl or silicon alkyl alkyl alkyl, or the non-interfering group with 1 to 20 carbon atom replaces.

3. claim 1 or 2 metal complexes, wherein R ^ABe alkyl, silicon alkyl alkyl,-oxyl substituted hydrocarbon radical, hydrocarbon amino-substituted hydrocarbyl, T is O or N.

4. the metal complexes of claim 3, wherein R ^ABe alkyl or silicon alkyl alkyl, T is O or N.

5. the metal complexes of claim 4, wherein R ^ABe alkyl or silicon alkyl alkyl, T is O.

6. the metal complexes of claim 3, wherein (R ^A) _j-T is dimethylamino, diethylamino, methylethyl amino, aminomethyl phenyl amino, dipropyl amino, dibutylamino, piperidyl, morpholinyl, pyrrolidyl, hexahydro-1 H-azepines-1-base, six hydrogen-1 (2H)-azocine base, octahydro-1H-azonine-1-base, octahydro-1-(2H)-azecinyl, methoxyl group, oxyethyl group, propoxy-, methyl ethoxy, 1,1-dimethyl oxyethyl group, trimethylsiloxy or 1,1-dimethyl ethyl (dimetylsilyl) oxygen base.

7. the metal complexes of claim 4, wherein (R ^A) _j-T group is methoxyl group, oxyethyl group, propoxy-, methyl ethoxy, 1,1-dimethyl oxyethyl group, trimethylsiloxy or 1,1-dimethyl ethyl (dimetylsilyl) oxygen base.

8. claim 1 or 2 metal complexes, wherein said one or more condensed ring or member ring systems contain heteroatoms on one or more rings, and it is N, O, S or P that this ring is gone up heteroatoms.

9. the metal complexes of claim 8, heteroatoms is N or O on the wherein said ring.

10. the metal complexes of claim 9, heteroatoms is N on the wherein said ring.

11. the metal complexes of claim 2, corresponding to following general formula: Wherein each symbol is previously defined.

12. the metal complexes of claim 11, corresponding to following general formula: Wherein each symbol is previously defined.

13. each metal complexes among the claim 1-12, wherein Z is-Z ^*-Y-, Z ^*With C _pBonding, Y and M bonding and

Y is-O--S-,-NR ^*-,-PR ^*-;

Z ^*Be SiR ^* ₂, CR ^* ₂, SiR ^* ₂SiR ^* ₂, CR ^* ₂CR ^* ₂, CR ^*=CR ^*, CR ^* ₂SiR ^* ₂, CR ^* ₂SiR ^* ₂CR ^* ₂, SiR ^* ₂CR ^* ₂SiR ^* ₂, CR ^* ₂CR ^* ₂SiR ^* ₂, CR ^* ₂CR ^* ₂CR ^* ₂, or GeR ^* ₂With

R ^*Be hydrogen independently of each other, or be selected from alkyl,-oxyl, silylation, haloalkyl, halogenated aryl and its bonded group, described R ^*Have at the most 20 non-hydrogen atoms and randomly from two R of Z ^*(work as R ^*When being not hydrogen) or the R from Z ^*With a R from Y ^*Group can form member ring systems;

Wherein p is 2, q is 0, M is in+the apparent oxidation state of 4 valencys, X is 1 for methyl, benzyl, trimethyl silyl methyl, allyl group, pyrryl or two X groups independently of each other together, 4-butane two bases, 2-butylene-1,4 two bases, 2,3-dimethyl-2-butylene-1,4-two bases, 2-methyl-2-butene-1,4-two bases or xylyl two bases.

14. each metal complexes among the claim 1-12, wherein Z is-Z ^*-Y-, Z ^*With C _pBonding, Y and M bonding and

Y is-O--S-,-NR ^*-,-PR ^*-;

Z ^*Be SiR ^* ₂, CR ^* ₂, SiR ^* ₂SiR ^* ₂, CR ^* ₂CR ^* ₂, CR ^*=CR ^*, CR ^* ₂SiR ^* ₂, CR ^* ₂SiR ^* ₂CR ^* ₂, SiR ^* ₂CR ^* ₂SiR ^* ₂, CR ^* ₂CR ^* ₂SiR ^* ₂, CR ^* ₂CR ^* ₂CR ^* ₂, or GeR ^* ₂With

R ^*Be hydrogen independently of each other, or be selected from alkyl,-oxyl, silylation, haloalkyl, halogenated aryl and its bonded group, described R ^*Have at the most 20 non-hydrogen atoms and randomly from two R of Z ^*(work as R ^*When being not hydrogen) or the R from Z ^*With a R from Y ^*Group can form member ring systems;

Wherein p is 1, and q is 0, and M is in+the apparent oxidation state of 3 valencys, and X is 2-(N, N-dimethyl) aminobenzyl, 2-(N, N-dimethylaminomethyl) phenyl, allyl group, methylallyl, trimethyl silyl allyl group.

15. each metal complexes among the claim 1-12, wherein-Z-is-Z ^*-Y-, Z ^*With C _pBonding, Y and M bonding and

Y is-O--S-,-NR ^*-,-PR ^*-;

Z ^*Be SiR ^* ₂, CR ^* ₂, SiR ^* ₂SiR ^* ₂, CR ^* ₂CR ^* ₂, CR ^*=CR ^*, CR ^* ₂SiR ^* ₂, CR ^* ₂SiR ^* ₂CR ^* ₂, SiR ^* ₂CR ^* ₂SiR ^* ₂, CR ^* ₂CR ^* ₂SiR ^* ₂, CR ^* ₂CR ^* ₂CR ^* ₂, or GeR ^* ₂With

R ^*Be hydrogen independently of each other, or be selected from alkyl,-oxyl, silylation, haloalkyl, halogenated aryl and its bonded group, described R ^*Have at the most 20 non-hydrogen atoms and randomly from two R of Z ^*(work as R ^*When being not hydrogen) or the R from Z ^*With a R from Y ^*Group forms member ring systems;

Wherein p is 0, and q is 1, and M is in+the apparent oxidation state of divalent, and X ' is 1,4-phenyl-1,3-butadiene, 1,3-pentadiene or 2,4-hexadiene.

16. each metal complexes among the claim 1-15, wherein M is the metal that is selected from one of one of one of 3-6 family, 7-9 family or 10-12 family.

17. the metal complexes of claim 16, wherein M is the metal of one of 3-6 family.

18. the metal complexes of claim 16, wherein M is the metal of one of 7-9 family.

19. the metal complexes of claim 16, wherein M is the metal of one of 10-12 family.

20. the metal complexes of claim 17, wherein M is a kind of metal of the 4th family.

21. the metal complexes of claim 20, wherein M is Ti.

22. the metal complexes of claim 20, wherein M is Zr.

23. the metal complexes of claim 21, wherein M is Ti, and is the apparent oxidation state of+4 valencys.

24. the metal complexes of claim 21, wherein M is Ti, and is the apparent oxidation state of+3 valencys.

25. the metal complexes of claim 21, wherein M is Ti, and is+the apparent oxidation state of divalent.

26. the metal complexes of claim 22, wherein M is Zr, and is the apparent oxidation state of+4 valencys.

27. the metal complexes of claim 22, wherein M is Zr, and is+the apparent oxidation state of divalent.

28. each metal complexes among the claim 13-27, wherein Y is-NR ^*

29. the metal complexes of claim 28, wherein R ^*For having and the uncle of N bonding or the group of secondary carbon(atom).

30. the metal complexes of claim 29, wherein R ^*Be cyclohexyl or sec.-propyl.

31. the metal complexes of claim 23, corresponding to following formula:

32. the metal complexes of claim 23, corresponding to following formula:

33. the metal complexes of claim 23, corresponding to following formula:

34. the metal complexes of claim 23, corresponding to following formula:

35. the metal complexes of claim 23, corresponding to following formula:

36. the metal complexes of claim 23, corresponding to following formula:

37. the metal complexes of claim 23, corresponding to following formula:

38. the metal complexes of claim 23, corresponding to following formula:

39. the metal complexes of claim 23, corresponding to following formula:

40. the metal complexes of claim 23, corresponding to following formula:

41. a catalyst system that is used for olefinic polymerization is prepared by the catalyst system component that comprises following component:

(A) a kind of catalyst component that comprises each metal complexes among the claim 1-40; With

(B) a kind of cocatalyst component that comprises active cocatalyst, wherein (A) and mol ratio (B) they are 1: 10,000 to 100: 1, or by using activating technology activation (A).

42. the catalyst system of claim 41 also comprises (C) aluminium organo-metallic component.

43. the catalyst system of claim 42, wherein aluminium organo-metallic component comprises aikyiaiurnirsoxan beta, aluminum alkyls or its mixture.

44. each catalyst system among the claim 41-43, wherein cocatalyst component comprises nonionic or ionic organoboron compound.

45. the catalyst system of claim 44, wherein cocatalyst component comprises three (pentafluorophenyl group) borine.

46. the catalyst system of claim 45, wherein cocatalyst component comprises aikyiaiurnirsoxan beta and three (pentafluorophenyl group) borine, and its mol ratio is 1: 1 to 5: 1.

47. each catalyst system among the claim 41-46 comprises that also (D) contains the carrier component of carrier substance, described carrier substance is polymkeric substance, inorganic oxide, metal halide or its mixture.

48. a catalyst system that is used for olefinic polymerization is prepared by the catalyst system component that comprises following component:

(A) a kind of catalyst component that comprises each metal complexes among the claim 1-40; With

(B) a kind of cocatalyst component that comprises active cocatalyst, wherein (A) and mol ratio (B) they are 1: 10,000 to 100: 1,

Wherein metal complexes is the radical cationic form.

49. an olefine polymerizing process comprises one or more C _2-20Alpha-olefin contacts with each catalyst system among the claim 41-48 under polymerizing condition.

50. the method for claim 49 is wherein with ethene, propylene and optional non-conjugated diene hydrocarbon copolymerization.

51. the method for claim 49 is wherein with ethene, propylene or ethene and propylene and one or more C _4-20Alpha-olefin copolymer.

52. each method among the claim 49-51, wherein this method is carried out in solution.

53. each method among the claim 49-51, wherein this method is carried out in gas phase.

54. each method among the claim 49-51, wherein this method is carried out in slurry.

55. the high temperature solution polymerization process of an olefin polymerization comprises one or more C _2-20Alpha-olefin under polymerizing condition with claim 41-48 in each catalyst body to tie up to temperature be to contact under about 100 ℃ to about 250 ℃.

56. the method for claim 55, wherein temperature is about 120 ℃ to about 200 ℃.

57. the method for claim 56, wherein temperature is about 150 ℃ to about 200 ℃.

58. polyolefin products by each method production among the claim 49-57.

59. the polyolefin products of claim 55, wherein product has 0.01 to 3 long-chain branch/1000 carbon atom.

60. the polyolefin products of claim 58, wherein product is for having comonomer distribution factor C _PfBe equal to or greater than 1.10 or molecular weight distribution factor M _PfBe equal to or greater than 1.15, perhaps comonomer distribution factor C _PfBe equal to or greater than 1.10 and molecular weight distribution factor M _PfBe equal to or greater than 1.15 copolymer compositions.

61. the polyolefin products of claim 60, wherein copolymer compositions has comonomer distribution factor C _PfBe equal to or greater than 1.20 or molecular weight distribution factor M _PfBe equal to or greater than 1.30, perhaps comonomer distribution factor C _PfBe equal to or greater than 1.20 and molecular weight distribution factor M _PfBe equal to or greater than 1.30.

62. each the part that contains cyclopentadienyl among the claim 1-40, wherein part is following form:

(A) has the free alkali of 2 protons that can remove;

(B) dilithium salt;

(C) magnesium salts; Or

(D) two negatively charged ion of list or dimethyl silanylization.

63. the part of claim 62 is used for each the purposes of metal complexes of synthetic production claim 1-40.

64. the part of claim 62 is used for synthetic purposes of producing the metal complexes of the metal that comprises one of the periodic table of elements the 3rd to 13 family, group of the lanthanides or actinium series and 1 to 4 part.

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