MXPA97003313A - Composite of cyclopentadiene replaced with a group containing heteroato - Google Patents

Abstract

The present invention relates to polysubstituted cyclopentadiene-containing compounds, at least one of whose substituents is of the form -RDR'n, wherein R is a linkage group between the cyclopentadiene and the group DR'n, D is a selected heteroatom of group 15 or 16 of the Periodic Table of the Elements or an aryl group, in which case R is at least the length of an ethylene group, R 'is a substituent and n is the number of R'united groups

Description

COMPOSITE OF CICLOPENTflDIENO REPLACED WITH AN OUE GROUP CONTAINS HETEROPHYTOMS DECRIPTTVQ MEMORY The invention relates to a polysubstituted cyclopen + adieno compound, at least one of which replaces + es is of the form -RDR ', -, in which R is a linkage group between the cyclopeotadiene and the group Ü' n, D is a het-eroatome selected from group 15 or 16 of the Periodic System of the Elements, R 'is a su + tiuent and n is the number of groups R' attached to D. fiqui hereafter, ci clopent ad eno will be represented by - the abbreviation Cp. That same abbreviation will be used for a cyclopen + adienyl group if it is evident, from the context, that it means the clopen-t adieno or its anion. Fn 1. of "Organo et.Chem., 479 (1994), 1-29, an analysis is provided on the influence of the substrates on cyclopentadiene as a ligand in metal complexes. On the other hand, the chemical and physical properties of metal complexes can be varied over a wide spectrum by adaptation of the constituents in the cyclopentadiene ring, on the other hand, it is stated that no predictions can be made concerning the effect What is to be expected for specific substituents Another assertion in this publication is "An important aspect of these catalytic systems is that tetravalent Ti centers are required to show catalytic activity." In this context, it should be taken into account. the fact that Ti is an example of the metals that are suitable as a metal in the metal complexes substituted with cyclopentadienyl in question. Surprisingly, it has now been found that they can be obtained These excellent catalytic components have a high activity in the polymerization of α-olefins if the Cp compounds according to the invention are used only as a ligand on metal which is not in its highest valence state. obtains a metal complex rnonosusti tuido with Cp of metals in a state of valence lower than the highest possible, in which the ligand containing Cp is rn? ltidentado-mona ionic and has a strongly stabilizing effect if block at the same time the sites complex assets, so that the complexes have an excellent Li tic tasting activity. A publication by Szyrnoma et al. in 3. Org. Chern. 1990, 55, 1429-1432 discloses a tetrasubstituted cyclopentadiene with methyl containing, as a fifth s? Sti +? Yente, a dL feml fosfi group which is linked to the Cp either directly or via an ethylene group. The synthetic method described is highly specific and nothing is said about whether Cp compounds substituted differently can be obtained, and if so, how. A publication by Jutzi et al. in Syn + hesie, 1993, 684, indicates that the Szymonial- 'et al. method, described above, produces mainly germinally substituted compounds, which can not be used as anionic ligands in metal complexes. The substituted substitution compounds of Cp ge are not suitable for use as a ligand and are not considered to be within the scope of the invention. DE-A-43.03.n47 describes Cs tetrasubstituted with methyl or ethyl groups and a group of the form RDR'n, in which R is a full rnet or e +? Ieno group and D is equal to 0, hl or S A publication by Bensley et al., In 1. Org. Chern., 1988, 53, 4417-4419, describes a Cs tetrasustido with methyl which contains, as a fifth substitution + e, a diphenylphosphine group which is attached to the Cp via a propylene group. A publication by Hafner et al., In Chernische Bepch + e, 1963, 661, 52-75 describes a Cp substituted with 2 adjacent methyl groups in combination with a dirnetiiammo group which is coupled to the Cp via? N group e + jleno. EP-0-0 416 815 discloses a Cs tetrasubstituted with methyl containing, as fifth its + ituent, an ethoxy group that is attached to the Cp via a full dimeric group. Hngew. Chem. I t. Ed. Engl. 1995. 34, p. 2266-226 ?, describes Cp which is substituted with a tert-butyl group and to which it is attached, at the same time, a rne-toxi or rneto i ethyl group. From none of the publications mentioned above those skilled in the art could deduce that the compounds according to the invention have a specific action as described above. The corresponding complexes in which the Cp compound is not substituted in the manner described are found to be unstable or, if they have been otherwise stabilized, they are found to provide less active catalysts than the complexes containing substituted Cp compounds in accordance with the invention, in particular in the case of the polymerization of a-oief i ñas. In addition, it is found that the Cp compounds according to the invention are capable of stabilizing highly reactive intermediates such as organometallic hydrocarbons, organic borohydrides, organometallic alkyls and organometallic cations. Moreover, they are suitable as stable and volatile precursors for use in the deposition of chemical vapor from metals. A polysubstituted Cp compound refers to a cyclopentadiene substituted with at least one group of the RDR O form and additionally with 1 to 4 R 3 * groups, which are defined hereinafter, not including the H or a substitute. + e. Two of these Rs groups can form a closed ring. Preferably, the polysifluid Cp contains at least 2 Ra groups as additional substitutents. When the Cp compounds thus substituted are present as a ligand in a metal complex, it is found that said complex becomes more suitable for the polymerization of α-olefms at a higher temperature than the complexes substituted with other Cp compounds. The Cp compound can also be a heterocyclopentadiene compound. Here, and hereafter, the expression "heterocyclopentadiene group" refers to a group which is derived from cyclopentadiene but in which at least one of the C-atoms of its 5-membered ring has been replaced by a heteroatom, heferoate or that can be selected from group 14, 15 or 16 of the Periodic Table of the Elements. If it is + to present + s of a heteroatom in the 5-membered ring, these heteroatoms may be identical or may be different. More preferably, the heteroatom is selected from the group 15 and even more preferably the heteroatom is f or fo. The heterocyclopentadiene ring can carry, depending on the number h of heteroa + omos, of 1 to (4-h) substituents R2. The groups R2, in each case and separately, can be hydrogen or a hydrocarbon-based radical containing 1-20 carbon atoms (such as alkyl, aplo, aralkyl, and the like). Examples of such hydrocarbon radicals are methyl, ethyl, propyl, butyl, hexyl, decyl, femyl, benzyl, and p-tolyl. Alternatively, two hydrocarbon radicals located close to each other can be linked together forming a cyclic system; Rz can also be a substitute that, in addition to or instead of carbon and / or hydrogen, contains one or more heteroatoms of groups 14 and / or L7 of the Periodic Slres of the Elements, without being directly linked by a heteroatom to Cp. Thus, a substitute can be a graph that contains F or Si. R2 may not contain a cyclopentadiemyl group or a group derived therefrom. The group R forms the link between the Cp and the group DR ', -. The length of the shortest link within Cp and D, referred to below as the main chain of R, is critical in that it determines the accessibility of the metal by the group DR ', -, in order to obtain, , the desired intramolecular coordination. A too small length of the group (or bridge) R may mean that, due to the deformation of the ring, the group ÜR'n can not be effectively coordinated. R has a length of at least? The group R may be a hydrocarbon group containing 1-20 carbon atoms (such as alkylidene, aplidene, aryl, and the like). Examples of such groups are ethylene, ethylene, propylene, b? Thieno, phenylene, with or without a substituted side chain. Preferably, the group R has the following structure; (-FR3,., -) "where p - 1 -4 and E is an element of group 14 of the Periodic System. The R3 groups are as defined for Rahnas hi-drogen. Consequently, the main chain of the R group, besides carbon, also contains silicon or germam.

Exemplary of such R groups are: dialkyl silicon, (JLalq? Ilgerrnylene, tet raaiq? Ildisilileno or tet ral uilsi l eti leño (-S? R 2.CR3i2-). The alkyl groups in such group referibly contain 1- 4 carbon atoms and, preferably, are a methyl or ethyl group The group DR ',, consists of? N heteroatorno D selected from group 15 or 16 of the Periodic System of the Elements and one or more s? St i +? R 'together with D. The number of groups R' (n) is related to the type of heteroatom D, in the sense that n = 2 if D belongs to group 15 and that n = 1 if D belongs to group 16 Preferably, the heteroatom D is selected from the group consisting of nitrogen (N), oxygen (0), phosphorus (P) or sulfur (S); more preferably, the heteroatom is nitrogen (N) .The R 'groups may be identical or different and you can choose between the same groups that have been defined to R2 with the exception of hydrogen.Preferably, the group R 'ee? n alkyl group, rnas pre fer-nally nickel, which contains 1-20 carbon atoms. More preferably, the R 'group is an n-alkyloyl containing 1-10 carbon atoms. Another possibility is that two groups R 'in the group DR'n are linked together to give a ring. The group DR'n ee can join by coordination link to a metal. If they are used as the only ligand that conforms Cp to a metal complex in which the metal is not at its highest valence state, it is found that Cp polysustide compounds provide compounds with good stability and good activity. catalytic Therefore, the invention also relates to said use and to the metal complexes obtained. Metal complexes that are catalytically active if one of their ligands is composed according to the invention are metal complexes of the 4-10 groups of the. Periodic System of Elements and rare earths (see the new notation of the 1UPAC found inside the cover of the Handbook of Chernistry and Physics, 70-1 edition, 1989/1990). In this context, preferably the metal complexes of groups 4 and 5 are used as a catalyst component to polypeptide olefins, the metal complexes of groups 6 and 7 additionally also for metathesis and ring-opening metathesis polymerizations and the complexes of metals of groups 8-10 for copol and defibrations of polar polarized materials, hydrogenations and carbonylations. Particularly suitable for the polymerization of polyoles are metal complexes in which the metal is selected from the group consisting of Ti, Zr, Hf ", V and Cr. The term define here, and hereinafter, refers to -olefins, diolefins, and other minerals, which are more often mentioned, if the expression polymerization of olefins is used, it refers to the polymerization of only one type of olefinic solvent or the copolunication of two or more olefins. , the invention also relates to the metal complexes thus composed, in which the metal is not in its highest state of valence, and to its use as cata lytic components, in particular for the polymerization of olefms, linear as well as branched olefms and cyclics and dienes which may or may not be conjugated, and mixtures thereof Preferably, the metal is selected from the group consisting of T (III), Zr (EII), Hf (TIl) and V (TV). That the substitutes join the Cp depends on the type of the Ra groups and the RDR's group. Sometimes it is possible to first bind the R2 substituents to the Cp and then the RDR'n group, and sometimes the reverse order is observed. Cp compounds substituted with a number of R 2 groups can be prepared, for example, by reacting a halide of the substituent compound in a mixture of the Cp compound and an aqueous solution of a base in the presence of a phase transfer catalyst. . It is possible to use virtually equivalent amounts of the halogenated substituent compounds with respect to the Cp compound. An equivalent quantity is understood as a quantity in moles corresponding to the desired multiplicity of substitution., for example 2 moles per mole of Cp compound if dissolution is desired with the subject system in question. Depending on the size and the impediment they are associated with the compounds that are going to be replaced, it is possible to obtain Cp compounds at the same time as + p substituted to substituted peptides. If a reaction is carried out with tertiary halides, as a rule only t-substituted Cp compounds can be obtained, whereas with primary and secondary halides it is generally possible to obtain tetra- and often even penta-s? Stit. Substituents which can be attached by means of this method are, for example, alkyl groups, both linear as branched, and cyclic, alkenyl and aralkyl groups. It is also possible that these contain, in addition to carbon and hydrogen, one or more heteroatoms of groups 14-17 of the Periodic Table of the Elements, for example, 0, N, Si or F. Examples of suitable groups are methyl, ethyl, isopropyl, sec-butyl, pentel, -hexyl and -octyl, tere-butyl and higher homologs, cyclohexyl, benzyl. The substituents are preferably used in the method in the form of their halides and preferably in the form of their bromides. If bromides are used, it is found that a smaller amount of phase transfer catalyst is sufficient and it will be found that a higher yield of the compound is obtained. By means of this method it is also possible, without isolation or intermediate purification, to obtain Cp compounds which are substituted with specific combinations of substituents. Thus, for example, first dissolution can be carried out with the aid of a certain halide and in the reaction mixture a third substitution with a different substance is added, a second halide being added to the mixture afterwards. of a certain time. This can be repeated, so that it is also possible to prepare Cp derivatives with three or more different substituents. The substitution takes place in a mixture of the Cp compound and an aqueous solution of a base. The concentration of the base in the solution is in the range between 20 and 80% by weight. The hydroxides of the alkali metals, for example K or Na, are extremely suitable as bases. The base is present in an amount of 5-30 moles, preferably 6-20 moles, per rnol of Cp compound. It was found that the reaction time can be shortened considerably if the solution of the base is renewed during the reaction, for example by first mixing the solution with the smaller components of the reaction mixture and some time later isolating the aqueous phase and replacing it. with a new quantity of the base solution. The substitution takes place at atmospheric or elevated pressure, for example up to 100 Upa, the latter in particular when volatile components are present. The temperature at which the reaction takes place can vary within wide limits, for example from -20 to 120 C, preferably between 10 and 50 QC. As a rule, it is appropriate to start the reaction at room temperature, the temperature of the reaction mixture then being able to rise as a result of the heat evolved in the course of the reaction. The substitution takes place in the presence of a phase transfer catalyst which is capable of transferring OH ions from the aqueous phase into the organic phase which contains Cp and the substituent compound. The OH ions react in the organic phase with a volume of H that can be cleaved from the compound of Cp. Possible phase transfer catalysts for use are ammonium, phosphome, arsonium, stibonium and bistrnutomo quaternary and tertiary sulfone salts. More preferably, ammonium and phosphonium salts are used, for example tricapplmethyl chloride, commercially available under the name Aliquat 336 (Fl? Ka AG, Switzerland, - General Mills Co., USA) and Adogen 464 (Aldrich Chemical Co., USA). Also, are suitable compounds such as benzyl + pet laronium chloride (TEDA) or benzyltrie-t-urnn bromide? io (TEBA-Br), benzyl rirnetiumlonium chloride, benzyl bromide ilarnome bromide or L >hydroxide; encà © là © rà © là ³ lonioonio (Triton B), tet anb? tilammonium chloride, tetra-n-butiiarnonio bromide, tet ra-n-b? tiiarnonio iodide, tet ra-nb? tilarnonio hydrogen sulfate or hydroxy or tetra-n-butylamide, and cetiitpme + i laronium bromide or cetilt chloride rirnet ilarnonio, benzyl pbutyl chlorides, tetra-n-pentii-, tetra-n-hexyl- and tpoctiipropyl- amoruo and his bromides. Useful phosphome salts include, for example, tributylhexadecylphosphonium bromide, ethylpheniphosphoxyl bromide, tetr phenylphosphonium chloride, benzyl phenylphosphine iodide, and tetrab-thiophosphonium chloride. It is also possible to use corona and cpptandoe as phase-transfer catalysts, for example, l5 ~ corona ~ 5, 18-corona-6, d? Benzo-18-corona ~ 6, d? C? Clohexane-18 ~ corona ~ 6, 4,7,13, 16, 21-? Entaoxa -l, 10-d? Azab? C? CloC8.8.5.Itr? Cosano (Kryptofix 221), 4,7,13,18-f etraoxa-l , 10-d? Azab? C? Chlor8.5.5le coeano (Kryptofix 211) and 4,7,13,16,21,24-hexaoxa-l, 10-iazabicycloCB, 8, 8] - hexacosane ("[2.2. 2-] ") and its benzoderi Kryptofix 222B. Polyethers such as ethylene glycol ethers can also be used as a phase transfer catalyst. The quaternary ammonium salts, phosphonium salts, phosphoric acid triarynides, crown ethers, polyethers and polyethers can also be used on supports such as, for example, on a crosslinked polystyrene? another polymer. The phase transfer catalysts are used in an amount of 0.01-2, preferably 0.05-1, equivalents based on the amount of Cp compound. To carry out the procedure, the components can be added to the reactor in various sequential orders. After the reaction is complete, the aqueous phase and the organic phase containing the Cp compound are separated. When necessary, the Cp compound is recovered by fractional distillation. An alternative preparation method for alkyl-substituted cyclopentadienes is one that proceeds via alkyl-substituted acetylenes with the aid of a titanium-catalyst, as described by C.M. Garner, Tet. Lett., Vol. 35, 1994, pp. 2463. Tetrahydrated tetrasubstituted cyclopentadienes can also be synthesized by reaction with 2-l? T? O-2-to quenos con? N ester, followed by ring closure to give the cyclopentadiene derivative, as described by DM Bensley, 3. Org. Chem., 53, (1988), 4417. According to the synthesis methods described above, however, only tetraalkylcyclopentadienes with 4 identical alkyl groups can be prepared. From acetylenes, it is also possible to prepare, with the help of tet racarbonyl-nickel, derivatives of CLclopentenone. The reaction of the cyclopentenone obtained with an alkyl-rne + al reagent (eg, alkyl lithium or a Gpgnard reagent), followed by water abstraction results in the corresponding dclopen-t-adieno derivative. However, via this route, only cyclopentaihene derivatives can be synthesized with 4 identical substitutes, as described by B. Fell, Chern. Ber. 109, (19P6), 2914. Cyclopentenones containing different alkyl groups can be synthesized by the reaction of Nazarov, with the use of ester (es), (3-unsaturated.) The obtained cyclopentenones can be converted, as described This reaction is described by Cyclopentadiene, Coma, Bul. Soc. Chi. France, 8-9, (1970), 2992. The cyclopentadiene derivatives can be converted into fulvene, which can be reacted with alkyl-metal reagents to give dclopentadiene derivatives with a higher degree of substitution (for this, see Stone K.J., 3. Org. Chein., (49), 1984, 1849). The group in the RDR ', joins a free position of the Cp compound previously substituted in one or more positions, for example according to the following synthetic route. During a first step of this route, a Cp compound substituted by reaction with a base, sodium or potassium is removed. Possible bases for use are, for example, organol + io (RaL?) Compounds or organo-magnesium compounds (R3MgX), wherein R3 is an alkyl, aryl or aral uilo group, and X is a halide, for example n-b? T? L-1-Ithio or i-propylnanesium chloride. Also, it can be used as a potassium hydrogen base, sodium hydride, inorganic bases, for example, NaOH and KOH and alkoxides and ami (Li, K and Na Juros.) Mixtures of the aforementioned compounds can also be used.This reaction can be carried out in a polar dispersant, for example ether. they are tetrahydrofuran (THF) or dibutyl ether.

Also, apolar solvents such as, for example, toluene can be used. Subsequently, during a second step of the synthesis route, the formed cyclopentadiemion anion reacts with a compound according to the formula (R'nD-R-Y), (XRY) or (XR-Sul), wherein D , R, R 'and n are co or have been defined here in Jo above. And it is a halogen wheel (X) or a sulfonyl group (Sul). Examples of halogen atoms X are chlorine, bromine and iodine. Preferably, the halogen atom X is a volume of chlorine or bromine atom. The sulfonyl group is of the form -OSO ^ R *, where R * is a hydrocarbon radical containing 1-20 carbons, eg, alkyl, aryl, aralkyl. Examples of such hydrocarbon radicals are butane, pentane, hexane, benzene, naphthalene. Instead of or in addition to carbon and / or hydrogen, R * may also contain one or more roatoms of groups 14-1? of the Sis + ea Periodic of the Elements, such as N, 0, Si or F. Examples of sulfonyl groups are: feni Irne-t anos? lfomlo, benzenes? lfomlo, 1-butanosulfonilo, 2,5 -speech obencenosul fonilo, 5 -dimet i lamino- i -naphthalenes? lfom lo, pentafluorobenzenesulfonyl, p-toluenesul fomlo, tpclo ometanosuJ fonilo, trifl? orometanosul fom lo, 2, 4, 6-tp isopropí lbencenosulfon lo, 2, 4,6 - tp? ne L-benzene-sulphonyl, 2- isosylidene, fonnyl sulphonyl, 4-rnet oxybenzenesulfonyl, 1-naphthalenesul fomyl, 2-naphthalene sulphonyl, e + anoeulonyl, 4-fl? Orobenzene? l foni Lo and 1-hexadecanosul foni lo. Pr otibly, the sulfonyl group is p-tol uenos? Lfomlo or tp fluoromethanes? Lfoni lo. S D is a nitrogen atom and Y is a sulfonyl group, the compound according to the formula (R'r, D-R-Y) is formed m by reaction of an aminoalcoholic compound (R's-NR-OH) with a baee (as defined hereinbefore), potassium or sodium, followed by a reaction with a halide of s? Lfomlo (Sul-X). The second reaction step can also be carried out in a polar dispersant, as described for the first stage. The temperature at which the reactions are carried out is between -60 and 80.C. Reactions with XR-Sul, XRY and with R'nD-RY, in which Y is Br or I, are normally carried out at a temperature between -20 and 20QC Reactions with R'r, DRY, in which And it is Cl, as a rule they are carried out at a higher temperature (10 to 80QC). The higher temperature-for the temperature at which the reactions are carried out is determined, in other factors, by the boiling point of the compound R'MD-R-Y and that of the solvent used. After the reaction with a compound according to the formula (XR-Sul) or (XRY), an additional reaction is carried out with L? DR'n or HDR'n to replace X with a DR'n- For this Finally, a reaction is carried out, optionally in the same dispersant as mentioned above, at a temperature of 20 to 80 ° C. In the course of this synthesis process, it is possible, when alkylating substituted Cp compounds, that Gemnal products are partly formed. A gerinal substitution is a substitution in which the number of substituted carbon atoms increases by one unit, but in which the number of replaced carbon atoms does not increase. The amount of gemine products formed is low if the synthesis is carried out by means of a substituted Cp compound that has 1 situitant and rises the more constituents it contains. the substituted Cp compound. In the presence of relatively large substituents in the substituted Cp compound, none or virtually any gerninal product is formed. Examples of sterically large substitutes are secondary or tertiary alkyl substituents. The amount of product gemina! Also formed is whether the second stage of the reaction is carried out under the influence of a Le? base whose conjugated acid has a dissociation constant with? n pK *. less than or equal to -2,5. The values of pK »are based on the reference of D.D. Perrin: Di ssociation Constant of Orqanic Bases ín Aaueous Solution, International Union of Puré and Applied Chernis + ry, Butterworf hs, London 1965. Values have been determined in aqueous solution of HOS0 ?. The ethers can be mentioned as an example of suitable d.ewis bases. If geminous products have been formed during the process according to the invention, these products can be separated in a simple manner from the non-gem products by conversion of the mixture of gem-and non-gem-substituted products into a salt, by reaction with potassium, sodium or a base, then the salt is washed with a dispersant in which the salt of the non-geminous products is more soluble or slightly soluble. The bases that can be used include the compounds mentioned above. Suitable dispersants are apolar dispersants such as alkanes. Examples of suitable alkanes are heptane and hexane. Other bridge systems can be synthesized from halides of (cyclopentadiemJ) d? Alk? lilsililo. The reaction of the alkyl halide with a nucleophile, for example dialkyl anhydrides, phosphides or lithium arsenites, results in a system with a silyl bridge with a donor heteroatom. Identically, it is possible to synthesize systems with dissimilar bridges. From the fulvenos, it is possible to synthesize-systems with bridges that contain a donor heteroatom and a carbon atom in the bridge, as D.M. Bensley, 3. Org. Chern., 53, (1988), 4417. The synthesis of metal complexes containing as a ligand the specific Cp compounds described above should be carried out according to the methods known per se for this purpose. The use of these Cp compounds does not require any adaptation of said known methods. Metal complexes supported on a vehicle can also be used. The polymerization of α-olefms, for example, ethylene, propylene, bietane, hexene, octene and mixtures thereof and combinations with dienes can be carried out in the presence of the metal complexes containing or binding the cyclopentadiem compounds. according to the invention. Particularly suitable for this purpose are the transition metal complexes, not in their higher valence state, in which only one of the cyclopentadiene compounds according to the invention is present as a ligand, and in which the metal is cationic during polymerization. These polymerizations can be carried out in the manner known for this purpose and the use of metal complexes with a catalytic component does not require any significant adaptation of these processes. The known polymerizations are carried out in suspension, solution, emulsion, gas phase or as a bulk polymerization. It is conventional to use, as cocatalyst, an organometallic compound, selecting the metal of group 1, 2, 12 or 13 of the Sis + ema Periodic of the Elements. Examples include t palq? Ilalumi nio, halides of alkylaluminium, alkylalumoxanes (such as rneti lalurninoxanos), + ps (penf-1af1? Oro em 1) bo ao, tetra (pent a-fluorophenyl) borate dunet i lamlimo or mixtures of they. The polymerizations are carried out at temperatures between -50QC and + 350QC, more particularly between 25 and 250QC. The pressures used are generally between atmospheric pressure and 250 MPa, for bulk polymerizations more particularly between 50 and 250 tlPa, for the polymerization processes between 0.5 and 25 MPa. Suitable dispersants and solvents are, for example, hydrocarbons such as pentane, heptane and mixtures thereof. Also worthy of consideration are aromatic hydrocarbons, perfluorinated opdonalinente. The monomer to be used in the polymerization can also be used as a dispersant or solvent. The invention will be explained with reference to the following examples, but it is not limited to them. The characterization of the products obtained was done by the following analytical methods. Gas chromatography (GC) was carried out on a Hewlett-Packard 5890 series II apparatus with a cross-linked HP silicone rubber column (25 in x 0.32 rn x 1.05 rnrn). Gas chromatography / mass spectrometry (GC-MS) was carried out with a Fisons MD80Q device equipped with a quadrupole mass detector, a Fisons AS800 toinjector and a CPSH8 column (30 rn x 0 , 25 mx 1 rnm, low purge). The NMR was carried out on a Bruker ACP200 device (? H = 200 MHZ; 3C ^ 5n MHz) or Bruker ARX-400 ("tH = 400 MHz; 3C ~ 100 MHz). To characterize the metal complexes, a Kratos MS80 mass spectrometer or alternatively a Finniga Mat 4610 was used.

".}. '? EXAMPLE I Preparation of Di (2-prQPil? CiclQpen + .atiier? > In a double-walled reactor with 200 nm volume, provided with deflectors, condenser, overhead stirrer, thermometer and addition funnel, 180 g of NaOH at 50% concentration, (2.25 moles) were combined, of course, 9.5 g of Aliquat 336 (23 ml) and 15 g (0.227 mol) of freshly cracked cyclopen + adieno. The reaction mixture was stirred turbulently at a speed of 1385 rpm for a few minutes. Then, 56 g of 2-propyl bromide (0.46 mol) was added, cooling with water taking place at the same time. A few minutes after the addition of the 2-propyl bromide, the temperature rose to approximately 10 ° C. Then, stirring was continued for 6 hours at 5QQC GC was used to indicate that at that time 92% of d (2-propyl) c? Clopentadiene was present in the mixture of di- and tp (2-propyl) cyclopentadiene. The product was distilled at 10 milliliters and 70QC. After the distillation, 25.35 g of d (2-propyD-cyclopentadiene were obtained.The characterization took place with the help of GC, GC-MS, i3C- and H-NMR.

E3E-1PLQ II Preparation of tri (2-Dr? DÍl) cycl? Pentadiene In a double-walled reactor with a volume of 200 rnl, provided with deflectors, condenser, overhead stirrer, thermometer and addition funnel, 180 g of 50% concentration NaOH (2.25 moles), of course, were combined. , 5 g of Aliquat 336 (23 ilirnoles) and 15 g (0,227 rnoLes) of freshly cracked clopentadLeno. The reaction mixture was stirred turbulently at a speed of 1385 rpm for a few minutes. Then, 84 g of 2-propyl bromide (0.68 mol) was added, cooling taking place with water at the same time. A few minutes after the addition of the 2-propyl bromide, the ternperamide increased to approximately 10 C. GC was used to indicate that approximately 30 minutes after the addition of all of the 2-bromide. ro? 2-propylcyclopentadiene (monosulfite) was formed. Then, the reaction mixture was heated to 50 ° C. After 2 hours, stirring was stopped and phase separation awaited. The aqueous layer was removed and 180 g (2.25 mol) of 50% NaOH concentration, freshly prepared, was added. The stirring was then continued for one hour at 50 ° C. GC was used to indicate that between 90 and 95% of tr (2-propyl) cyclopentadiene was present in the mixture of di-, tri- and tetra- (2-propy-D-cyclopentadiene) The product was distilled at 1.3 After the distillation, 31.9 g of tp (2-? ro? 1) cycloperitadiene were obtained.The characterization took place with the help of GC, GC-MS, 3C- and Hl-NMR. .

EXAMPLE III Preparation of tetraf2-propyl) cyclopentadiene The method was analogous to that of Example II, but now 114 g of 2-propyl brornium (0.93 mol) were added and after 7 hours the aqueous layer was replaced a second time.

At the same time, an additional 5 g (12 rnilirnoles) of Aliq? At 336. After, heating took place for 16 hours at 55QC. GC was used to indicate that at that time 85% of tetra (2-propyl) cyclopentadiene was present in the mixture of tp- and tetra (2-prop? 1) cyclopentadiene. The product was distilled 1.0 nuil bar and B8-90OC. After the distillation, they were obtained 34.9 g of tetraf 2-pro?) C? Clopentadiene. The characterization took place with the help of GC, GC-MS, 3C- and * H ~ NMR.

EXAMPLE IV Preparation of dif cyclohexyl) ci clooentadiene A double-walled reactor, with a volume of 1 liter, provided with deflectors, condenser, overhead stirrer,? -F thermometer and addition funnel, was charged with 600 g of 50% concentration NaOH (7.5 mol. ), of course, and then cooled to 8SC. Then 20 g of Aliq? At 336 (49 rnilunoles) and 33 g (0.5 rnilirnoles) of freshly cracked cyclopen + adiene were added. The reaction mixture was stirred turbulently for a few minutes. Then 172 g of cyclohexyl bromide (1 g) was added, 05 rnil irnoles), taking place cooling with ice at the same time. After 2 hours of stirring at room temperature, the reaction mixture was heated to 70 ° C and then stirred for a further 6 hours. GC was used to indicate that 79% di (cyclohexyl) c? Clopentadiene was present at that time. The product was distilled at 0.04 inil and 110-120QC. After distillation, 73.6 g of di (cyclohexyl) ci-pentadiene were obtained. The characterization took place with the help of GC, GC-MS, 13C- and? -.- NMR.

EXAMPLE V Preparation of di-tri t3-pentyl) cyclopen + adienr > A double-walled reactor with a volume of 1 liter, provided with deflectors, condenser, overhead stirrer, thermometer and addition funnel, was charged with 430 g (5.4 moles) of NaOH at 50% concentration, clear. Then 23 g (je Aliquat 336 (57 milliols) and 27 g (0.41 mol) of freshly cracked cyclopen + adiene were added in. The reaction mixture was stirred turbulently for a few minutes, then 150 g of bromide was added. 3-penfyl (1.0 mole) over a period of 1 hour, cooling taking place with water at the same time After 1 hour of stirring at room temperature, the reaction mixture was heated to 70 ° C and then The mixture was stirred for an additional 3 hours, the stirring was stopped and the phase separation was waited, the aqueous layer was removed and 540 g (6.70 mol) of freshly prepared concentration 50% NaOH were added and thereafter stir for an additional 4 hours at 70 ° C. GC was used to indicate that at that point the mixture consisted of di- and tp (3-pentiDciclopentadiene (approximately 3: 2) .The products were distilled at 0.2 military, 51OC and 0, 2 military, 77-80QC, respectively. After the distillation, they were obtained 32 g of di- and 18 g of tp (3-pent? I) c? Clopentadiene. The characterization took place with the help of GC, GC-MS, 3C- and ^ H-NMR.

EXAMPLE VI Preparation of trif cyclohexyDcyclopentadiene A double-walled reactor with a volume of 1 liter, provided with baffles, condenser, overhead stirrer, thermometer and addition funnel, was charged with 600 g of NaOH at 50% concentration (7.5 mol), clear, and then it cooled to 8QC. Then, 20 g of Aliq? At 336 (49 rnilL oles) and 33 g (0.5 .mol) of freshly cracked cyclopentadiene were added. The reaction mixture was stirred turbulently for a few minutes. Then, 256 g of cyclohexyl bromide (1.57 mol) were added, cooling taking place with water at the same time. After 1 hour of stirring at room temperature, the reaction mixture was heated to 70 ° C and then agitated an additional 2 hours. After 2 hours, the stirring was stopped and the phase separation was quenched. The aqueous layer was removed and 600 g (7.5 mol) of freshly prepared concentration 50% NaOH was added, followed by stirring for an additional 4 hours at 70 ° C. GC was used to indicate that 10% di- and 90% of t r? (C? Clohexa 1) c? Clo ~ pentad? E in the mixture was present at that time. The product was distilled at 0.04 milliliters and 130QC. After distillation, 87.4 g of tp (cyclohexyl) cyclopentadiene were obtained. The characterization took place-cor, the help of GC-, GC-MS, 3-3C- and H-NMR.

EXAMPLE VII Preparation of di 2-butyl) cir: lopentadiene A double-walled r-actuator with a volume of 1 liter, provided with deflec + ores, condenser, top agitator, 20 Thermometer and addition funnel was charged with 600 g of 50% NaOH concent ac (7.5 mill.), clear, and then cooled to 10SC. Then, 30 g of Aliquat 336 (74 rnilunoles) and 48.2 g (0.73 rnols) of freshly cracked cyclopentadiene were added. The reaction mixture was stirred turbulently for a few minutes. Then, 200 g of 2-butyl bromide (1.46 rnoles) were added over a period of half an hour, with cooling taking place with water at the same time. After 2 hours of stirring at room temperature, the reaction mixture was heated to 60 ° C, and then stirred for 4 additional hours. GC was used to say that at that time 90% di (2-butii) c? Clopentadiene were present in the mixture. The product was distilled at 20 milliliters and 80-90PC. After distillation, 90.8 g of di (2-buty1) cyclopen-t-adiene were obtained. The characterization took place with the help of GC, GC-MS, iBC- and H-NMR.

EXAMPLE VIIT Preparation of trif -butyl) ci pentadienn A double-walled reactor with a volume of 1 liter, equipped with deflectors, condenser, top stirrer, thermometer and addition funnel, was charged with 400 and NaOH at 50% concentration (5 rnilirnoles), clear. Then, 9.6 g of Aliquat 336 (24 rnili oles) and 15.2 g (0.23 rnols) of freshly cracked cyclopenf adiene were added. The reaction mixture was stirred with turbulence for a few minutes. Then 99.8 g of 2-butyl bromide (0.73 mol) were added over a period of one hour, cooling with water taking place at the same time. After a half hour of stirring at room temperature, the reaction mixture was heated to 70 ° C and then stirred for an additional three hours. The stirring was stopped and phase separation awaited. The aqueous layer was removed and 400 g (5.0 rnols) of 50% concentration NaOH, freshly prepared, was added, and then it was stirred for an additional two hours at 70 ° C. GC was used to indicate that at that time it was present more than 90% of tr? (2-but? L) c? Clopentadiene in the mixture of di-, tri- and tetra (2-b? TL) c? Clo? Entad? Ene. The product was distilled to 1 balance and 91OC. After distillation, 40.9 g of tr? (2-but? I) c were obtained? clopentadiene. The characterization took place with the help of GC, GC-MS, -t3C- and - ^ H-NMR.

EXAMPLE IX Preparation of di-vif 2-oenti Dei clopgn + a ^ ftrMr A double-walled reactor with a volume of 1 liter, provided with deflectors, condenser, overhead stirrer, thermometer and addition funnel, was charged with 900 g (11.25 nouns) of NaOH at 50% concentration, clear. Then, 31 g of Aliquat 336 (77 thousand uñóles) and 26.8 g (0.41 rnoles) of freshly cracked cyclopentadiene were added. The reaction mixture was stirred urulently for a few minutes. Then, 155 g of α-β-bromide (1.03 5 moles) was added over a period of 1 hour, cooling with water taking place at the same time. After 3 hours of stirring at room temperature the reaction mixture was heated to 70 ° C, and then stirred for a further 2 hours. The agitation stopped and the separation waited of phases. The aqueous layer was removed and 900 g (11.25 moles) of 50% concentration NaOH, freshly prepared, was added, and then an additional two hours at 70 ° C was added. GC was used to indicate that at that time the mixture consisted of di- and t p- (2-pentyl) -cyclopen-t-adiene (approximately 1: 1).

The products were distilled to 2 soldiers, 79-81 oc and 0.5 mili bars, 102OC, r-spectacle. After distillation, 28 g of di- and 40 g of t ri (2-penf il) cyclopentadiene were obtained. The characterization took place with the help of GC, GC-MS, 13C- and XH-NMR. 0 EXAMPLE X Preparation of di t 2-propyl) cyclohexyl 1 cyclopentadi T 150 g of NaOH at 50% concentration (1.9 mole) were combined in a double-lane reactor with a volume of 200 nm, deflector tank, condenser, overhead stirrer, thermometer and addition funnel, of course, 7 g of Aliquat 336 (17.3 mmolnyl) and 8.5 g (0.13 mol) of freshly cracked cyclopentadiene. The reaction mixture was stirred turbulently at a rate of 1385 rprn for a few minutes. Then 31.5 g of 2-propyl bromide (0.26 mol) were added, cooling with water taking place at the same time. The incorporation took a total time of 1 hour. After the addition of the bromide, the reaction mixture was heated to 50 ° C. After 2 hours, stirring was stopped and phase separation was awaited. The aqueous layer was removed and 150 g (1.9 rnols) of fresh 50% concentration NaOH ai were added. Then 20.9 g (0.13 mol) of cyclohexyl bromide were added and then stirring was continued for an additional 3 hours at 70 ° C. GC was used to indicate u at that time 80% of d (2-propy1) cyclohexylocyclopontadiene was present in the mixture. The product was distilled at 0.3 millibar and 80OC. After distillation, 17.8 g of di (2-propyl-1) cyclohexylcyclopentadiene were obtained. The characterization took place with the help of GC, GC-MS, 3C-- and H-NMR.

EXAMPLE XI Preparation of tetrafoctil) c? ClQPentadiene A double-walled reactor with a volume of 1.5 liters, provided with deflectors, condenser, overhead stirrer, thermometer and addition funnel, was charged with 900 g of 50% NaOH concentration (11.3 moles), clear , and then cooled to 10OC. Then, 30 g of Aliquat 336 (74 thousand imoles) were added and 48 g (0.72 mol) of freshly cracked cyclopentadiene was added. The reaction mixture was stirred turbulently for a few minutes. Then, 577 g of octyl bromide (2.99 moles) was added over a period of one hour, taking place cooling with ice at the same time. After 1 hour of stirring at room temperature, the reaction mixture was heated to 35 ° C and then stirred for a further 6 hours. The stirring was stopped and phase separation awaited. The aqueous layer was removed and 920 g (11.5 rnols) of fresh concentration 50% NaOH was added, and then it was stirred for an additional 5 hours at room temperature. GC was used to indicate that at that time 10% of tp-, 83% of tetra- and 7% of pentafoctil) c were present in the mixture. clopentadiene. The product was distilled under reduced pressure. After distillation under vacuum, 226.6 g of tetrafoc + al) -cyclopentadiene were obtained. The product was characterized with the aid of GC, GC-MS, 3C- and J-H-NMR.

EXAMPLE XII Preparation of tetraf-propyl) cyclin dienentane A double-walled reactor with a volume of 1 liter, provided with deflectors, condenser, overhead stirrer, thermometer and addition funnel, was charged with 1000 g of NaOH at 50% concentration (12.5 mol), of course, and then cooled to Ldoc. Then 30 g of Aliquat 336 (74 rnilunoles) and 50 g (0.75 moles) of freshly cracked cyclopentadiene were added. The reaction mixture was stirred turbulently for a few minutes. Then 373 g of propyl bromide (3.03 rnoles) were added over a period of one hour, cooling with ice taking place at the same time. After 1 hour of stirring at room temperature, the reaction mixture was heated to 35 ° C and then stirred for a further 6 hours. The agitation was stopped and phase separation awaited. The aqueous phase was removed and 990 g (12.4 mole) of 50% concentration NaOH, freshly prepared, was added, followed by stirring for an additional 5 hours at room temperature, GC was used to indicate that at that time L4% of tri-, 80% of tetra- and 6% of pent (propyl) cyclopentadiene was present in the mixture.After vacuum distillation, 103.1 g of tetra (propyl) c? clopentad were obtained? The product was characterized with the aid of GC, GC-MS, ^ C ~ and H-NMR EXAMPLE XIII Preparation of dif 2-phenylpropyl) cyclopentadiene A double-walled reactor with a volume of 1 liter, equipped with deflectors, condenser, overhead stirrer, thermometer and addition funnel, was charged with 600 g of NaOH 50% concentration (7.5 moles), of course, and then cooled to 8OC. Then 20 g of Alaquat 336 (49 inylimols) and 33 g (0.5 moles) of freshly cracked cyclopentadiene were added. The reaction mixture was stirred turbulently for a few minutes. Then 219 g of 1-broino -2-feml propane (1.1 mole) were added, at one time, cooling taking place with water at the same time. After 2 hours of stirring at room temperature, the reaction mixture was heated to 70 ° C and then stirred for a further 6 hours. GC was used to indicate that 89% of d? (2-feml? Rop? L) c? Clopentadiene was present at that time. The product was distilled under high pressure and alpha temperature, resulting in 95.34 g (0.4 mol, 80%) of di (2-fempropiD-cyclopentadiene.) The product was characterized with the help of GC, GC-MS , AaC- and * H-NMR.

EXAMPLE XIV Preparation of dif 1.l-dimethylpropiDciclopentad ene A double-walled reactor with a volume of 1 liter, equipped with deflectors, condenser, supepor stirrer, thermometer and addition funnel, was charged with 600 g of 50% concentration NaOH (7.5 rnoles), clear, and then It cooled to 8OC. Then, 20 g of Aliq? At 336 (49 rni limoles) and 33 g (0.5 rnoles) of cic opent were added to freshly cracked Leno. The reaction mixture was stirred turbulently for a few minutes. Then, 226.6 g of 2-brorno-2-met? Butano (1.5 moles) were added, all at once, cooling taking place with water at the same time. After 2 hours of stirring at room temperature, the reaction mixture was heated to 70 ° C and then stirred for a further 6 hours. GC was used to indicate that at that time 56% of d? (L, 1-d? Rnet? Iprop? 1) c? Clopentadiene was present. The product was distilled at low pressure and high temperature, yielding 47.7 g (0.23 rnols, 46%) of d (l, l-dimethylpropyl) c) clopentadiene. The product was characterized with the help of GC, GC-MS, C- and '-H-NMR.

EXAMPLE XV Preparation of di-l-methyl-l-ethylproDi) cyclopentadiene This preparation was carried out as in the preceding example, but now with: 247.6 grams of 3-bromo-3-rnetipenten. In the first case, 55% and after distillation, 43% (50.4 grams) of d (1-rnet? L-l-ef and Ipropyl) cyclopentiene were obtained.

EXAMPLE XVI In situ preparation of 2-fN. N-dimethylaminoi tosylate i lo) In dry nitrogen, a solution of n-butyllithium in hexane (1 equivalent) in dry THF (addition time: 60 minutes), at -10 ° C, was added to a solution of 2-dithrene-n-ethanol (1 equivalent). ) in a three-necked round bottom flask, equipped with a magnetic stirrer and an addition funnel. After addition of all of the buf-lithium, the mixture was brought to room temperature and stirred for 2 hours. Subsequently, the mixture was cooled (-10 ° C) and then p-tolosenosulfonyl chloride (1 equivalent) was added and then stirred for 15 minutes at this temperature, before adding the solution to a cyclopentadieyl anion.

By a similar method, comparable tosylates can be prepared. In some of the following examples, a tosylate is in each case coupled with alkylated Cp compounds. In the course of said coupling, the required substitution reaction is accompanied by gerninal coupling. In almost all cases it was possible to separate the geminous isomers from the non-geminous isomers by conversion of the non-geminous isomers into their sparingly soluble potassium salt, this salt then being washed with a solvent in which said salt is insoluble or sparingly soluble.

EXAMPLE XVII to. Preparation of f dimethylaminoetiDdicic Iohexi lci clopentadienn In a nitrogen atmosphere, a solution of n-butyllithium in hexane (18.7 ml, 1.6 moles / liter, rilirnols) was added dropwise to a cooled solution (OOC) of dicyclohexyl-cyclopentadiene (Example TV) (6.90 g, 30.0 mmol) in dry rahydrofuran (125 nl) in a 250 ml three-necked round bottom flask equipped with a magnetic stirrer and an addition funnel. After 24 hours of stirring at room temperature, 30.0 rnilirnoles of 2- (d? Met? Lam? Noet? Io) tosa lato prepared in situ were added. After 18 hours of stirring, the conversion was found to be 88% and water (100 ml) was carefully added to the reaction mixture and then fetrahydrofuran was removed by distillation. The crude product was extracted with ether and then the combined organic phases were dried (sodium sulfate) and evaporated to dryness. The residue was purified on a column of silica gel, which gave CILO as a result 7.4 g of (irnetilammoet i Ddiciclo-he i lcyclopentadLeno. h. Synthesis? _ _ JClQrurP S. 1- f dimethylaminoethyl) -2,4-di-cyclohexylcyclopentadienyltitaniof III) and Ethyldinylamino-et i 11-2.4-dicyclohexylcyclohexanediylidenethritol of TTT? rCsH5. (c-C4H) s (CH2) 2NMe - ,; Tl (III) ClE,] and CCaHa (c-C * H1.í.) a. (CH2.}.? Np? aTi (III) Mea] In a Schlenk-r-az-rna, 1.37 g (4.54 mmol) of (di-ethylamino-1-di) -cyclohexylchloride was dissolved in 30 ml of diethyl ether. ico and then the solution was cooled to -60OC. Then, 2.84 ml of n-butyl-1-liter (1.6 M in hexane, 4.54 rnil-imoles) were added dropwise. The reaction mixture was brought slowly to room temperature and then stirred for 2 hours. After evaporation of the solvent, a yellow powder remained, to which 30 tn1 of petroleum ether was added. In second Schlenl flask > - 40 ml of tetrahydrofuran was added to 1.68 g of Ti (III) C13.3THF (4.53 p limols). Both Schlenfc flasks were cooled to -60 ° C and then the organolithium compound was added to the suspension of T (III) Cla. Then, the reaction mixture was stirred for 18 hours at room temperature, after which the solvent was evaporated. To the residue, 50 rnl of petroleum ether was added, which was subsequently evaporated to dryness. Was a green solid that contained 1- (dimethylarninoet.il) -2,4-d? C? Clohex dichloride? I read clopentad? emlt? tan? o (IIT). In a Schlenl-mat, 0.31 g (0.671 millilimols) of the di- (di-nitronylene glycol) -2,4-dicyclohexylcyclopentadienylthi (111) dichloride, descpt or above, were dissolved in 30 mL of diethyl ether. The solution was cooled to -60 ° C and then 0.73 ml (1.84 M in diethyl ether, 1.34 rni limoles) of inethyl-1 if io were added dropwise. The solution was brought slowly to room temperature and then stirred for 1 hour. Then, the solvent was evaporated and the residue was extracted with 40 ml of petroleum ether. The filtrate was concentrated by boiling and dried for 18 hours in vacuo. 0.14 g of a blackish brown oil containing T l- (dimeti la inoetii) -2,4-dicyclohexylcyclopentadienyl dirnetylitamide (ITI) were left, as a residue.

EXAMPLE XVIII - Preparation dS tdimethylaminoethyl) dif2-p * Hvtil) c lOr.g-? Vt - * - < ____ In a nitrogen atmosphere, a solution of n-butyllithium in hexane (24.0 rnl; 1.6 rnols / 1; 38 rmlimoles) to a cooled solution (OQC) of di- (2-pentiDciclopentadieno (7.82 g; 38.0 mmol) in dry tetrahydrofuran (125 nmol) in a 250 nl three-necked round bottom flask equipped with a magnetic stirrer and an addition funnel. After 24 hours of stirring at room temperature, 2- (dimethyl-amino-ethyl) tosylate (38.0 mmol) prepared in situ was added. After 18 hours of stirring, the conversion was found to be 92% and water (100 ml) was carefully added, dropwise, to the reaction mixture and then tetrahydrofuran was distilled off. The crude product was extracted with ether and then the combined organic phases were dried (sodium sulfate) and evaporated to dryness. The residue was purified on a column of silica gel, which yielded 8.2 g of (dirnet i lammoethyl) d (2-pentyl) c? Clopen Ene. h- Synthesis (dichloride £ l = 1- dimeti lammoethyl) -2 4-d? 7-nent 11) cyclopentadienyltitanium f III) i? Cl- dimeti laminoet i 1) -? .4-rt? 1 -ßßnt i 1) ci clopentadienyl -dimetiltitaniof TTT) CC5H2 (c -CaHxl) to i CH «) ^ Me ^ Ti. { p T) Cl »] and CC5H2 (c-C.sH J.) ^ (CHs») ¡aNMeSÍT? (IIT) M © »1 In a Schlenk flask, 1.60 g (5.77 mmol) of (di-ethylamino-1) d (2-? Ent? I) c? Clopentadiene were dissolved in 40 ml of diethyl ether and then the solution was cooled to -60 ° C. Then, 3.6 rnl of n-b? T-lithium (1.6 M in hexane, 5.77 mmol) was added dropwise. The reaction mixture was brought slowly to room temperature and then stirred for 2 hours. In a second Schlenl flask - 40 rnl of tetrahydrofuran was added to 2.14 g of T? (III) C13.3THF (5.77 rniliols). Both Schlenk flasks were cooled to -60 ° C and then the organolithium compound was added to the TifllDCla suspension. Afterwards, the reaction mixture was stirred for 18 hours at room temperature, after which the solvent was evaporated. To the resin, 50 ml of petroleum ether were added, and subsequently evaporated to dryness, leaving 1.60 g of solid green containing 1- (dimethylaminoetii) dichloride -2.4- as residue. d? (2-pent? l) c? clopentad? in? l? tan? o (111) In a Schlenk flask, 0.33 g (0.835 mmol) of l- (di-di-ethyarninoethyl) d? 2-pentyl) c? Clopentad? In? L? Tan? O (111) in 40 ml of diethyl ether The solution was cooled to -60 ° C and then 0.90 g of inet-lithium (0.25 g) was added dropwise. 1.84 M in diethyl ether, 1.66 mL) The reaction mixture was taken slowly to room temperature and followed by stirring for 1 hour, then the solvent was evaporated and the residue was extracted with water. of petroleum ether and the filtrate was heated to a boil) 0.24 g of a dark brown oil containing Cl-di-ethylaminoethyl) -2,4-d? 2-pentyl) was left as a residue. ? clopentad? in? l? d? rnet? lt? tamo (III) "EXAMPLE XIX to. Preparation _ £ (dimethylaminoethyl) tri f 2 -prooi i) G.? clopenta- A solution of 62.5 nln of n-butyl-lithium (1.6 M in n-hexane, 100 nrnrnol) was added to a 500-ml dry flask with a magnetic stirrer. dry nitrogen atmosphere, to a solution of 19.2 g (100 mmol) of tetrahydrochloride in 250 rnl of THF at -60 ° C After heating to room temperature (in about 1 hour) stirring is continued for 2 additional hours. After cooling to -60 ° C, a solution of dirnetiiainmoetyl tosylate (105 rni limoles), prepared i sit? Was added over a period of 5 minutes. The reaction mixture was warmed to room temperature and then stirred overnight. After adding water, the product was extracted with petroleum ether (40-60OC). The combined organic layers were dried (Na 3 SO), and evaporated under reduced pressure The conversion was higher than 95% The product yield after distillation (based on triisopropylcyclopentadiene) was about 55%. b. Synthesis of dichloride of [-1 - (dirnet ilarninoet-i 1-) -? .3.5 - 1 r i (? ~ DroDiDcicloDentadieniltitaniodlI) Cl- (dirnethyl-arm noet? D- 2.3.5- tp. (2-prop? 1) cyclopentadienyl 3d.rnet? T? Tan? .o (TTT) CCsH (i ~ Pr) a (CH! 2) ::, NMes.Ti. (III) ClS! And CCsHd-PrJafCHaíaMMeaTj (IlDMea In a 3-necked 500-milliliter flask, 200 ml of petroleum ether were added to 8.5 g (28.18 mmol) of 1- (dirnetyl-1-inlet) -2, 3, 5-p (-propyl) Cyclopentadienyl potassium In a second 3-neck flask (1 liter), 300 ml of tetrahydrofuran was added to 10.5 g (28.3 milli-nols) of T (III) Cl 3. 3THF. Both flasks were cooled to -60 ° C and then the organopotassium compound was added to the suspension of T (III) Cla. The reaction mixture containing 1- (direthylarninoetyl) -2,3,5-tr? (2-propyl) -cyclopentadienyl t-nitin (EII) dichloride was brought slowly to room temperature, after which stirring was continued for an additional 18 hours. Then, it was cooled to -50 ° C. and then 30.6 ml of the dialkyl lithium (1.827 M in diethyl ether, 55.9 inyl ynol) was added. After 2 hours of stirring at room temperature, the solvent was removed and the residue was dried in vacuo for 18 hours. To the product, then 700 rnl of petroleum ether was added and then filtered. The filtrate was concentrated by boiling and dried in vacuo for 2 days .. 9.2 g of a brownish black oil containing Cl- (direthylarninoethyl) -2,3,5-tr? 2-propyD-cyclopentadienyldimetiititamoam remained as a residue. Eli).

EXAMPLE XX to. Preparation of (di-n-butylaminoethyl) di f 2-ocylyl cyclonen-tadiene The reaction was carried out in a manner identical to that used for (di-ethylaminoethyl) -d? - (2-pentyl) c? Clopentadiene, the tosylate being prepared from N, N-di-n-butylamethanol in situ The conversion was 88%. The d? - (n-butylaminoetyl) -d? - (2-pentyl) c? Clopentadiene was obtained after purification on a preparative column on silica gel using, in turn, petroleum ether (40 g. -60 ° C) and THF, followed by distillation under reduced pressure, with a yield of 51%. b. Preparation of d-lpp-rP of 1-fdi-n-butylaminoethyl) -2.4- < J. (2-pen? L) ci iopentadienilti aniptIII? L "CaHa (2-C?» H t):;, (H.2)? N (n-C-H «, 2T? Íiti) Cla] In a Schlen flask, 0.919 g (2.54 rni limole) of (d? -n-but? Lam? Noet? L) d? (2-pentyl) c? Clopentadiene was dissolved in 40 ml. diethyl ether and then, the solution was cooled to -60 ° C. Then, 1.6 nrn of n-butyllithium was added dropwise. (1.6 M in hexane, 2.56 mmol). The reaction mixture was brought slowly to room temperature and then stirred for 2 hours. Then, this was added, at -60 ° C, to 960 ing (2.59 mmol) of TiII III) C13.3THF in 20 rnl of tetrahydrofuran. Then, the reaction mixture was stirred for 18 hours at room temperature, after which the solvent was evaporated. The residue was washed with 10 rnl. There remained, as residue, 0.95 g of solid green containing l- (di-n-buffalolethyl) -2,4-d- (2-pen-t-Ll) cyclopentadienyl-titanium III dichloride) ., LO EXAMPLE XXI 1 * Preparation S t dimethylaminoethyl) di t 2-propyl) ci nnnenadieno L5 The reaction was carried out in a manner identical to that used to prepare (dirnetiia inoetil) -tri- (2-? Rop? L) ci - clopentadiene. The conversion was 97%. The diethexyl moeti ldn sopropilcyclopentadiene was obtained by distillation, with a yield of 54%. h- Synthesis _ = dichloride of Cl- f dimet lam noe i 1) - .4-di f 2-propyl) c clopentad enthylthiaph III) i¿ Cl-f dimethylaminoetn) -2,4-df 2 -propyl) cyclopentadienyldimetil tanrofTTT ) rcaH2 (? Pr) 2 (CH2) aT? (III) Cl23 and [CsH2 (? Pr) 2 (CH2) T? (IIT) rie2] To 8.9 g (40.3 rnilirnoles) of (dirnetilammoethyl) -d? ~ (2-propyD-cyclopentadiene in 100 ml of tetrahydrofuran in a 3-neck 250-ml flask, 25.2 rnl was added dropwise. of n-butyl-lithium (1.6 M, 40.3 mmol) In a second 3-necked flask (500 mL), 100 mL of tetrahydrofuran was added to 14.93 g (40.3 mmol) of Ti (III) C13.3THF Both flasks were cooled to -60OC and then the organolithium compound was added to the suspension of T (III) C] 3. The reaction mixture containing dichloride of 1- (dirnet) lammoeti i) ~ 2,4-d? (2-propyl) c? clopentad? in? lta? tam (III) was brought slowly to room temperature, after which stirring was continued for an additional 18 hours. at -60 ° C and then 50.4 ml of rnetii-lithium (1.6 M in diethyl ether, 80.6 mmol) was added.After 2 hours of stirring at room temperature, the solvent was separated and the residue was removed. Dry in vacuum for 18 hours, then add gave the product 350 ml of petroleum ether and filtered. The filtrate was concentrated by boiling and dried under vacuum for one day. Was left, as residue, 11.6 g of brown / black oil containing Cl-idimethylaminoeti 1) -2, 4-d? (2-? Ro? L) c? Clopenta- 4- ' d? en? l] d? rnet? ltitan? o (ITT).

EXAMPLE XXII to. Preparation of imeti aminoethyl) di f2-butyl) cyclopentadiene In a nitrogen atmosphere, a solution of nb? T-1-lithium in hexane (31.2 ml, 1.6 rnoles / liter, 50 inylirols) was added dropwise to a cooled solution (OOC) of d? (2-butyl) cyclopentadiene (8.90 g, 50.0 mmol) in dry tetrahydrofuran (150 ml) in a 250 ml round bottom flask provided with? n magnetic stirrer and an addition funnel. After stirring for 24 hours at room temperature, the 2- (dirnethylaminoquinhex) tosylate (50 g) was added., 0 millirnoles). After stirring for 18 hours, the conversion was found to be 96% and water (100 rnl) was added dropwise, carefully, to the reaction mixture and then the tet rah drofan rano was distilled off. The crude product was extracted with ether and then the combined organic phases were dried (sodium sulfate) and concentrated to boiling. The residue was purified on a column of silica gel, which resulted in 8.5 g of (di-ethylaminoethyl) di (2-butyl) cyclopentadiene. b. Synthesis of 1-fdimethylaminoethyl) -. 4-dif -hu-ti1) cyclopentadienyltitaniof III) - y dichloride. C1- fdime ilami noethyl) -2.4- di f 2-butyl) cyclopentadienyl3dimethylthiitaniofIII) CCßHaí2-C * H ^), (CHa), NM? ATl (ETI) Cl »1 and rCaHa (2-C- * H-») aiCHa) aNMeaTl (TII) M? al In a Schlen flask, 2.36 g (9.48 rnilirnoles) of (di ethylaminoeti l) d were dissolved? (2 ~ b? T? L) c? Clo? In 50 mg of diethyl ether and then the solution was cooled to -60 ° C. Then 5.9 ml of n-butyl lithium (L, 6 M in hexane, 9.44 yl) was added dropwise. The reaction mixture was slowly brought to room temperature and then stirred for 2 hours. In a second Schlen flask, 50 ml of tetrahydrofuran was added to 3.51 g of TiIIII) Cla.3THF (9.44 rnilirnoles). Both Schlenk flasks were cooled to -60 ° C and then the organoyl compound was added to the suspension of Ti (III) Cl = ,. Then, the reaction mixture was stirred for 18 hours at room temperature, after which the solvent was evaporated. To the residue, 50 rnl of petroleum ether was added, which was subsequently evaporated to dryness. 2.25 g of a green solid containing l- (dirne iia inoetii) -2,4-d dichloride remained as a residue. (2-but Dciclopenta-dieniltitanioflII). In a Schlenk flask, 0.45 g (1.22 rnilirnoles) of l- (dirnef ilarninoethyl) di (2-butyl) c-clopentad-erul-t-tan (TII) dichloride (TII) were dissolved in the flask. ml of diethyl ether. The solution was cooled to -60 ° C. and then 1.33 ml of dimethyl lithium (1.84 M in diethyl ether, 2.44 mmol) was added dropwise. The reaction mixture was brought slowly to room temperature and then stirred for 1 hour. The solvent was then evaporated. The residue was extracted with 50 rnl of petroleum ether and the filtrate was concentrated by boiling. They remained, as residue, 0.36 g of a blackish brown oil containing Cl- (d? RnetLiam? Noet? L) -2,4-d? (2 ~ b? T? I) -cyclopentadienilldirnef? Lt ? ta? o (pi). 10 EXAMPLE XXIII a- Preparation of fdimethylaminoethyl) ri f2-butyl) cyclopentadiene The reaction was carried out in an identical manner to that described for (di eti LainmoetiDtp (2-? Ro? L) cyclopentadiene The conversion was 92% .The product was obtained by distillation, with yield of 64%. b. Synthesis of [1-f-dimethylaminoethyl) -2.3.5-trif2-butyl) cyclopentadienyltitaniof III) Cl-f imeti1-aminoe i 1) -2 3-R-tri f 2 -butyl) cyclopentadienylIdi ethyltitaniof III) rC5H ( 2-C H -,) r -. (CHa?) ZNMea l (TII) Cla and rCsH (2-C * H,) a (CHa «NM? Ari (lII) M? A -) f. In a 500 ml 3-neck flask, 200 rnl of petroleum ether was added to 6.28 g (20.6 mmol) of 1- (dirnet 11 arnideneeti 1) -2, 3, 5-tp (2-butyl) ) Cyclopentadieni1 -potassium. In a second 3-neck flask (1 liter), 300 ml of tetrahydrofuran was added to 7.65 g (20.6 millimoles) of Ti (III) Cla.3THF. Both flasks were cooled to -60 ° C and then the organopotassium compound was added to the suspension of TL (III) Cla. The reaction mixture containing the dichloride of L- (di-ethylaminoethyl) -2, 3, 5-tp (2-butyl) c? Clopentin? In? Lt? Ta-n? O (III) I take it slowly to room temperature, after which the agitation is continued for an additional 18 hours. Then it was cooled to -60 ° C and then 22.3 ml of rilethyl lithium (1.827 M in diethyl ether, 40.7 ml of urn) were added. After 2 hours of stirring at room temperature, the solvent was separated and the residue was dried under vacuum for 18 hours. Then, 700 nrl of petroleum ether was added to the product and then filtered. The filtrate was concentrated by evaporation and dried in vacuo for 2 days. 7.93 g of a brownish black oil containing Cl- (dunethylari oethyl) -2,3,5-? (2-butyl) c? Clo? Entad? In? L] d ?? net remained. lt? tan? o (III).

EXAMPLE XXIV Preparation of f diptetilaminoetiD di f 3-nent i 1) ic1 nn > ntad enn The reaction was carried out in an identical manner to that described for (dirnetilarninoe-t? L) d? (2-? Rop? L) c? Clo? Enf adieno. The conversion was 99%. The (dirnet i lammoetii) di (3-pentyl) c? -clopentadiene was obtained after purification on a preparative column on silica gel using, successively, petroleum ether (40-60OC) and THF, the yield being 85% EXAMPLE XXV Preparation of f-di-n-butylaminoethyl) -di-f3-pentyl) cyclopentadiene The reaction was carried out in a manner identical to that described for (d? -n-but? Iam? Noet? I) d? (2-pentyl) c-clopenf-a-diene .. The conversion was 95%. The product was obtained after purification on a preparative column on silica gel using, successively, petroleum ether (40-60 ° C) and THF, the yield being 75%.

EXAMPLE XXVI Preparation of f 2-dimethylaminoethyl) -trif3-pentyl 1) cyclopentediene The reaction was carried out in a manner identical to that described for (direthylaminoetyl) tp (2-propyl) c-clopentadiene. The conversion was 94%. The (2-d? Met? Larn? Noethyl) -tr? - (3-pentiDciclopentadieno) was obtained after purification on a preparative column on silica gel using, successively, petroleum ether (40-60OC) and THF, being the 61% yield.

EXAMPLE XXVII _ * Preparation of cyclohexylfdimethylaminoethyl) -di-f 2-propyl) - In a Schlenl container < , at room temperature, a solution of n-butyltin in hexane (25.0 mmol, 1.6 mmol / L, 40.0 mmol) was added dropwise to a solution of cyclohexyl-diusopropylcyclopentadiene. (9.28 g, 40.0 mmol) in dry THF (150 mL). Then, in another Schlenk flask, a solution (hexane-thiohexyl in hexane (25.0 mmol, 1.6 mmol / liter, 40.0 mmol) to a cold solution (~ 78 mL) was added dropwise. of dimethylethenoethanol (3.56 g, 40.0 mmol) in THF (100 mL) After one and a half hours of stirring at room temperature, the mixture was again cooled to -78 ° C and the chalk was added slowly. solid (8.10 g, 40.0 rnilirnoles) The mixture was brought to 0 ° C, stirred for 5 minutes in the procedure, cooled back to -78 ° C and then the mixture of the first Schlenl flask was added at once. After 16 hours of stirring at room temperature, the conversion was 100% After column chromatography, 11.1 g of cyclohexyl (dunet i lapunoet 11) -di- (2-? Rop? L) CLClopent diono. b. Synthesis of 1-f-dimethylaminoeti 1) -4-cyclohexy-1, 2,5-dif2-propyl) cyclopentadienyltitaniof III) d-dimethylaminoethyl) -4-cyclohexyl-2,5-di-2-prooyl dichloride ldimetiltitanioflll) CCßH (cH? x) (2-CaHt aíCH ^) yNM? sT? (ITT) 01a] and rCaH (cH? x) (2-C3H-) (CH; 2) s? NMe «T? (IIl ) Mea] A (fjirnetilarninoet il) c? clohex? ld? (2-? rop? l) cyclopenta-dieml-lithium (2.18 g, 7.20 mmol), dissolved in 20 nr of tetrahydronane, was added a cooled suspension (-70OC) of T? (III) Cla.3THF (2.57 g, 7.20 my limols) in 20 rnl of THF. The dark green solution formed was stirred for 72 hours at room temperature. After being concentrated by boiling, 30 ml of pet oil ether 40-60 was added). After evaporating to dryness once more, a green powder (2.37 g) was obtained, which contained l- (dn-di-amino-in.-ethyl) -4-c-clohexyl-2, 5-d dichloride. (-propyl) cyclopentadiem l-titamoí III). [lithium chloride], To a suspension, cooled to -70 C, of 0.63 g (1.36 mmol) of [1- (d? et? lam? noet? i) -4-c? clo dichloride. -hexy 1-2,5 -di (2-propyl) cyclopentadienylthioamine III) 1. [lithium chloride] obtained above in 30 rnl of diethyl ether, 1.70 ml of rnet i] -ii were added dropwise. Uncle (1.6 M in diethyl ether (2.72 milliols) The greenish brown suspension darkened immediately, then the mixture was stirred for 1 hour at room temperature, concentrated to dryness by boiling and dissolved in 40 ml. of petroleum ether After filtration and complete evaporation of the solvent, a black powder (0.47 g, 1.22 rnilirnoles) containing 1- (dimethylarnmoethyl) -4-c? clohex? -2 was obtained, 5-di (-pro? L) c? Clopentad? In? Ld? Met? Lt? Tan? O (Til).

EXAMPLE XXVIII Preparation of fdi-n-butylaminoethyl) dif2-propyl) cyclopentadiene The reaction was carried out in a manner identical to that described for (dimethylammoethyl) di (2-propyl) c? Clo? Enfadiene, with the N, N-d? -n-butylamine tosylate being prepared in situ? oethanol The conversion was 94%. Non-native di-n-butyla moeti ldi (2-propyl) c? Clopentadiene was obtained by distillation with a yield of 53%.

EXAMPLE XXIX Preparation of f-methylaminoethyl) -tn-f 2-pentyl) cyclopentadiene The reaction was carried out in a manner identical to that described for (d? Methyla? Noet? L) fr? (2-propyl J-cyclopontadiene.The conversion was 90%. (Dirne ilarmnoe il) -tp- ( 2-pent? L) cyclopentadtene was obtained after purification on a preparative column on silica gel using, successively, p.sub.β + RP (40-60OC) and THF, the yield being 57%.

EXAMPLE XXX to. Preparation r_e. bisf dimethylaminoetiDtriisopropi lcyclo-pen-tadieno In a dry three-necked 500-ml flask equipped with a magnetic stirrer, a solution of 62.5 nl of n-butyl-lithium (1.6 M in n-hexane, 100 rnilirnoles) was added to the atmosphere. of nitrogen, to a solution of 19.2 g (100 mlles) of tp isopropylcyclopentadiene in 250 ml of THF at -60OC. After heating - at room temperature (approximately 1 hour) the stirring was continued for an additional 2 hours. After cooling to -60 ° C., a solution of dirnetaaminoethyl (105 mmol) prepared in situ was added over a period of 5 minutes. The reaction mixture was warmed to room temperature and then agglutinated overnight. After adding water, the product was extracted with petroleum ether (40-60OC). The combined organic layers were dried (a ^ O ^) and evaporated to dryness under reduced pressure. The conversion was greater than 95%. A portion of the product thus obtained (10.1 g, 38.2 rmlimoles) was alkylated under the same conditions with dirnet ilarnmoetyl cough (39.0 rni limoles). The b? S (2-d? Met? Lam? Noet? L) tr? Soprop? Lc? Clopentadiene was obtained with a yield of 35% via column chromatography. h. Synthesis of [1,3-bistdimethylane-n-ethyl ester] -2.4 F-ri (2-propyl? Cyclopentadienyl i aniQ (III) - - [1.3-t »? S (dime-il-ami noet i1) -2.4.5- tri (2-proDi) cyclopentadienyl-ldimeti 1 i ta-nio (III) [Caf2-CaH-) 3 ((CHa) aNMea Tl (III) C] a] and [Ca (2-C3H7) a (iCHa) aNMea ) aTl (TII) Mea] In a 3-necked 500-milliliter flask, 200 milliliters of petroleum ether were added to 3.38 g (10.1 milliliters) of l, 3-bs (d-rhenethylaminoethyl) -2.4, 5- r? (2-? Rop? L) c? Clo? Entad? In? L-potassium. In a second 3-neck flask (1 Liter), 300 ml of tetrahydrofuran was added to 3.75 g (10.1 mmol) of Ti (IIT) Cla.3THF. Both flasks were cooled to -60 ° C and then the organopotassium compound was added to the suspension of T (Ill) Cl 3. The reaction mixture containing 1- (d? Rnet? Lam? Noet? L) -2, 3, 5-tr dichloride? (2-propyl) c? Clopentad? In? -t? Tan? O (III) was brought slowly to room temperature, after which stirring was continued for an additional 18 hours. It was then cooled to -60 ° C and then 11.0 rnl of ethyl lithium (1.827 M in diethyl ether, 20.1 mmol) was added. After 2 hours of stirring at room temperature, the solvent was removed and the residue was dried in vacuo for 18 hours. The product was then added with 700 rnl of petroleum ether and then filtered. The filtrate was concentrated by boiling and dried in vacuo for 2 days. 3.62 g of a brownish black oil containing 1, 3-b? S (d? Net? L -amnoethyl) -2,4,5-tp (2-ropil) c? clopentadiem ll iinetLl titanium (III).

EXAMPLE XXXI -. Preparation _ (di-ethylaminoethyl) tricyclo-hexylc-r.lopenta- _i___ The reaction was carried out in a manner identical to that described for (dimethylamino-methyl) -diocyclohexylcyclopenthene. The conversion was 91%. The product ß was obtained via preparative column purification on silica gel using, successively, petroleum ether (40-60OC) and THF as eluyenfe, the yield being 80%. b. Synthesis dfi Ci-H-irO d = 1-f dimethylaminoet i 1) -2.3.5- riciclQhexiiciclgpentadieniI-tianip (III) u. [i-fdimet i-aminoethyl) -2.3.5-tricyclohexylcyclopentadienyldimetiltitaniotlIT) [CBH (c-H? X) 3CH) aNMeaTl (ITI) Cla] and [CaH (c-H? x) aICHa) aNM? aTl (III) Me2] A (direthylarninoethyl) tpccyclohexylcyclopentadienylthio (2), 11 g, 5.70 mL), dissolved in 20 ml of tetrahydrofuran, a cooled suspension (-70 ° C) of T (III) Cl. 3 THF (2.11 g, 5.70 millilimols) was added in 20 ml. of THF, at -70OC. The dark green solution formed was stirred for 72 hours at room temperature. After being concentrated by boiling, 30 rnl of petroleum ether (40-60OC) was added. After evaporating to dryness once more, a mint-colored powder (2.80 g) was obtained, which contained dichloride of 1- (diinetiia inoet? I) -2, 3, 5-tp cyclohexylcyclopentadienyl tLtan? or (III). To a solution, cooled to -70 ° C, of 0.50 g (0.922 milliliters) of [dichloride of 1 - (dirnetylarninoethyl) -2, 3, 5-tp cyclohexylcyclopentadiem 1 -titaniof III) 3. [lithium chloride] , obtained above, in 30 rnl of diethyl ether, 1.15 rnl of rethyllithium (1.6 M in diethyl ether, 1.84 rniliols) were added dropwise. The greenish brown suspension darkened immediately. Then, the mixture was stirred for 1 hour at room temperature, concentrated by boiling to dryness and dissolved in 40 rnl of petroleum ether. After filtration and complete evaporation (with solvent), a black powder (0.40 g, 0.87 rn.monoles) containing 1- (dinethylaminoeti-1-R-cyclohexy-cyclopentadienyl-Ti (111) -dirnetium) was obtained.

EXAMPLE XXXII to. Preparation dS (di-n-butylammoethyl) -tri-2-pentyl) cyclopenium adieno The reaction was carried out in a manner identical to that described for (di-n-butylaminoethyl) -d? - (3-? Ent? I) c? Clopentadiene. The conversion was 88%. EL (2 ~ d? -n- b? Tilarninoeti i) -d? - (2-pentiDciclopentadieno was obtained after purification on a preparative column on silica gel, using, successively, petroleum ether (4Q-60QC) and THF, followed by distillation under reduced pressure, with a yield of 51%. ÍL. Sís esis dS icloruro dS 1- fdi-n-butiI aminoethyl) -2.3. s-tri f 2-pentyl) cyclopentadienyltitaniof III) CaH (2-CaH A 3 (CHa a (n- u) aTl f III) Cía] 2,633 g (6,11 millirnoles) of (di-n-β-tilane-N-di-di- (2-pentyl) -cyclopentadiene were dissolved in 50 ml of diethyl ether and cooled to -78 ° C. Then 3.8 tons of n-but were added. 1-γ (1.6 M in hexane, 6.11 nil irnols) After stirring for 18 hours at room temperature, the light pale yellow solution was concentrated by boiling and then washed once with 25 ml of petroleum ether, then the solvent was completely evaporated, leaving behind 1.58 g of a yellow oil containing l- (d? -n-butyl-inethyl) -2, 3,5-t? 2-pent-Di-cyclopentyl-lithium Then the organolithium compound was dissolved in 50 ml of tetrahydrofuran and added at -78 ° C. to 9.23 g (24.9 mmol) of Ti (III) C13.3THF. After 50 hours of stirring at room temperature, a dark green solution had formed, and after having completely boiled this solution, they remained, residue, 1.52 g of? n green oil containing l- (d? -n-butylaminoethyl) -2, 3, 5-t r (2-pentiicyclopentadienyl-titaniof III).

EXAMPLE XXXIII to. Preparation of fdimethylaminoethyl) etrae ilcyclopentadiene In a Schlen flask, a solution of n-butyl-1-io in hexane (6.00 ml, 1.65 mol / l; 9.90 rni limles) to a solution of tetraethylcyclopentadiene (2.066 g; 11.6 mmol) in dry THF (20 mmol) at room temperature. 51 Then, in a second Schlenk flask, a solution of n-butyl lithium in hexane (5.90 ml, 1.65 moles / liter, 9.74 ml limes) was added dropwise to a cold solution ( -78OC) of 2-dirneti larninoethanol (0.867 g, 9.74 inylimols) in THF (35 rnl). After stirring for several hours at room temperature, the mixture was again cooled to -78 ° C and solid tosylate chloride (1,855 g, 9.75 mmol) was added slowly. The mixture was taken to OOC, stirring for 5 minutes in the process and the mixture of the first Schlenk flask was added all at once. After 16 hours, the conversion was 100%. After column chromatography, 2.6 g of (dirneti larní noet i L Ref raethylcyclopentadiene. b. Chloride synthesis dS l- < dimethylaminoe il) -2.3. .5-te-Rethyl-cyclopentadienyltitanium III) v [1-f dimethylamine no.1) -2.3.4.5-tetraethylcyclopentadiene? 3-dimethyl-titanium-IIT) rCsE (CHa) aNMe2Tlf IIT) Cla3 [CaEt * (CHa) a »NM? 2TlIIIII) M? to] In a Schlenk flask, 0.38 g of (direthylamine noethetraefl-cyclopentadiene (1,523 nilimols) in 20 ml of diethyl ether and then the solution was cooled to -60 ° C. Then, 0.95 ml of n-butyl-Jithium (1.6 M in hexane) was added dropwise. 1.52 inylirols) After 30 minutes, the cooling was stopped and then stirred for 1 hour at room temperature In a second Schlenk flask, 30 ml of tetrahydrofuran at 0.57 g (1.538 thousand LNN) were added. ) of Ti (III) C13.3THF Both Schlen flasks were cooled to -60 ° C and then the organolithium compound was added to the TidlDClg suspension, then the reaction mixture was stirred for 18 hours at room temperature, then from which the solvent was evaporated.To the residue, 50 ml of petroleum ether was added, which was subsequently evaporated to dryness.The residue was a green solid containing 1- (dirhanediiarninoethyl) dichloride -2, 3, 4, 5 ~ tetraethylcyclopentad? emlt? tan? o (III), 20 ml diethyl ether was added tyl at 0.25 g (0.68 nilimoles) of the product. After cooling to -60 ° C, 0.85 ml of ethyl lithium (1.6 M in diethyl ether) was added.; 1,36 rnilirnoles) and then stirred for 3 hours at room temperature. Then, the solvent was removed under reduced pressure. After the addition of petroleum ether, filtration and boiling concentration, 0.17 g of a dark oil containing l -f (dimethylaminoet.il) -2,3, 4,5-tetraet lcicl opentadleni 13dirnet11tita i oU was obtained. II).

EXAMPLE XXXIV to. Pre-arac tion dS (dimethylaminoethyl) te ra-n-octylcyclopenta- _i___ In a Schlen flask, a solution of n-but 11-11 thio in hexane (24.8 rnl, 1.6 moles / liter, 39.6 mmol) was added dropwise to a solution of tetra-n-oct. ? ic? clopenf.ad? ene (20.4 g; 39.6 rni limol) in dry THF (100 rnl) at room temperature. Then, in a second Schlen flask, a solution of n-butyllithium in hexane (24.6 ml, 1.6 rnoles / liter, 39.6 mmol) to a solution (-78QC) was added dropwise. 2-Dirnetyl Ineth Nol (3.53 g, 39.6 mmol) in THF (30 mL). After two hours of stirring at room temperature, the mixture was again cooled to -78 ° C. and the solid tosyl chloride (7.54 g, 39.6 thousand imols) was added slowly. The mixture was brought to OOC, stirring for 5 minutes in the procedure and then the mixture of the first Schlenk flask was added all at once. After 16 hours, the conversion was 87%. After the column chromatography, 19.2 g of (direthylamidoeti 1) tetra-n-octylcyclopentadiene were obtained.

EXAMPLE XXXV a- F dimethylaminoet? l) tetra-n-prop? l ciclonentA- < _) ___ To a solution of tetra-n-propylcyclopentadiene, a solution of n-butyl-lithium in hexane (93.8 ml, 1.6 moles / liter, 150 ylnol) was added dropwise to a solution of tetra-n-propylcyclopentadiene in a 3-necked 500-ml flask. (35.0 g, 150 mmol) in dry THF (200 rnl) at room temperature. Then, in a second Schlenk flask, a solution of n-butyllithium in hexane (93.8 rnl, 1.6 rnols / liter, 150 rnilinols) was added dropwise to a cold solution (-78OC) of 2 g. -d? methanol? noethanol (13.35 g; 150 rni limole) in THF (100 ml). After two hours of stirring at room temperature, the mixture was again cooled to -78 ° C and solid tosyl chloride (28.5 g, 150 rnilunoles) was added slowly. The mixture was brought to -20 ° C, stirring for 5 minutes in the process, and then the mixture of the first Schlenk flask was added. After 16 hours, the conversion was 97%. After column chromatography, 39.6 g of (dimethylmethyl) tetra-n-propylcyclopentadiene were obtained. b- Synthesis of 1-fdimethylaminoethyl dichloride) -7. .4.5-tetra-n-propylcyl clonentadienyltitanium III) i¿ [1- f dimethylane i 1) - 7.3.4.5-tetra-n-propylcyclopentad? In? LJdimetiltitaniof TTT) [C5 (n-Pr) ^ (CH: a ) il, NMe2T? (III) Cls] and [cS n ~ F »r-5 - + (CH?) ^ NMe2T? (III) MeZ! 3 In a Schlenk flask, 0.62 g of (dinethylane noetii) tetra (n-? Ro? 1) cyclopentadiene (2.03 mmol) were dissolved in 20 ml of diethyl ether, and then the solution was cooled to - 60OC. Then, 1.27 ml of n-butyllithium (1.6 M in hexane, 2.03 rmlirnoles) was added dropwise. After 30 minutes the cooling was stopped and then stirred for 1 hour at room temperature. In a second Schlenk flask, 30 rnl of tetrahydrofuran was added to 0.75 g (2.03 ml limole) of TL (III) C13.3THF. Both Schlenl 'flasks were cooled to -60OC and then the organolithium compound was added to the suspension of TL (III) C1-After, the reaction mixture was stirred for 18 hours at room temperature, after which the solvent was evaporated . To the residue, 50 rnl of petroleum ether was added, which was subsequently evaporated to dryness. The residue was a green oil that contained dicloride l - (dirnet Iole 11) -2, 3, 4, 5-tet ra-n-prop? Lc? Clopentad? In? Lt.Ltan? O (TII ). 20 ml of diethyl ether was added to 0.51 g (1.01 rnilirnoles) of the product. After cooling to -60 ° C, 1.26 ml of distillyl lithium (1.6 M in diethyl ether, 2.02 rmlirnoles) was added and then stirred for three hours at room temperature. Then, the solvent was removed under reduced pressure. After adding petroleum ether, filtering and concentrating by boiling, 0.31 g of a dark oil was obtained, containing l- [(dimethylamethyl) -2, 3, 4, 5-tef ran-propi lei clopentadieml 3d ? rne-t? lt? fan? o (lll).

EXAMPLE XXXVI Preparation _ = (dimethylaminoethyl) dif 2-phenylproni 1) cyclopentane-tadiene 12.5 rnl of a 1.6 -nolar solution of n-butyl were added dropwise. 1 -1 Lt in hexane to a cooled solution (OQC) of d? - (2-phenolyl) c? Clopentadiene (6.05 g; 20.0 milliards) in dry tetrahydrofuran (100 rnl), in a nitrogen atmosphere, in a 250 ml, three-necked round bottom flask equipped with a magnetic stirrer and an addition funnel. After 24 hours of stirring at room temperature, a solution of 2- (dι-rα-γ-l-n-yl) tosylate (20.0 ylimoles), prepared in situ, in THF / hexane was added. After 18 hours of stirring, it was found that the conversion was 90% and water (100 rnl) was added drop by drop, carefully, to the reaction mixture and then the tetrahydrofuran was distilled off. The crude product was extracted with ether and then the combined organic phases were dried (sodium sulfate) and concentrated by boiling. The residue was purified on a column of silica gel, which gave 5.98 grams (80%) of (dimet 11 to moet 11) di (2 -fe ilpropyl) c? clopentadiene.

EXAMPLE XXXVII Preparation d = dichloride dS f f dimethylaminoeti 1) di f 7-phenylpropii? cyclopentadienil Ki anio A (dirneti lamí noe il) di (2- femlpropí 1) cyclopentadiene (1.12 grams, 3 mmol), dissolved in 20 ml of tetrahydrofuran, was added 1.87 ml of a 1.6 -nolar solution of b? til-lithium in hexane, to OOC (ice bath). After 15 minutes of stirring, this mixture was further cooled to -78 ° C. and a suspension, also cooled to -78 ° C., of T (ITI) Cl: 3.3THF (1.1 g, 3 mmol) in 20 ml of water was added. THF The cooling bath was removed and the dark green solution formed was stirred for 72 hours at room temperature. After having been concentrated by boiling, 30 ml of petroleum ether (40-60) were added. After evaporating to dryness once more, a green powder (1.19 g) was obtained, containing dichloride of ((dirnethylamino-noethyl) d (2-phenylpropyl) cyclopentadiem Ritanium.

EXAMPLE XXXVIII to. Preparation of f dimethylaminoetiDdif 1.1-dimethyl propyl) cyclo-nentadiene ml of a 1.6-nanolar solution of n-butyllithium in hexane was added dropwise to a cooled solution (OOc) of d? - (l, ld? Et? Lprop? L) c? Clo? Entad? (8.25 g, 40.0 ml) in dry tetrahydrofuran (125 ml) in a nitrogen atmosphere, in a round-bottom, three-neck, 250-ml ratio, equipped with an agitator magnetic and an addition funnel. After 24 hours of stirring at room temperature, a solution of 2- (direthylarninoethyl) tosylate (40.0 mmol), prepared in situ, was added. in 58 THF / hexane. After 18 hours of stirring, the conversion was found to be 91% and water (100 ml) was added dropwise, carefully, to the reaction mixture and then the tetrahydrofuran was removed by distillation. The crude product was extracted with ether and then the combined organic phases were dried (sodium sulfate) and concentrated by boiling. The residue was purified on a column of silica gel, which yielded 9.1 grams (82%) of (dunethylamine noethyl) d? (1, 1-dirnet ilpropyl) cyclopenthene.

£ -. Synthesis dS dichloride d & (t dimethylaminoeti1) di 11.1 -dimethylpropyl) cyclopentadienyl) titanium A (dimet i larní noet 11) d? (L, l-dirnet i Lpropí l) ci clopenta-diene (1.39 grams, 5 thousand irnols), dissolved in 20 rnl of tetrahydrofuran, added 3.1 ml of a Solution of butyl lithium in hexane 1.6 rnolar to OOC (ice bath). After 15 minutes of stirring, this mixture was further cooled to -78 ° C and a suspension was added, which was likewise cooled to -7-BOC, T je (III) Cl3.3THF (1.86 g, 5 -nilirnoles) in 20 rnl of THF. The cooling bath was removed and the dark green solution formed was stirred for 72 hours at room temperature. After having been concentrated by boiling, 30 ml of petroleum ether (40-60) was added. After evaporating to dryness once more, a green powder (1.68 g) was obtained, containing d (methylene? Netheyl) dichloride (Jirnet? Lprop? L). ) c? clo? entad? in? l) - titanium.

EXAMPLE XXXIX a-, Preparation dS tdimetilaminomethyl) di f l-met i i -1 -ethylpropyl) ci l opentadiene The preparation was carried out as in Example XXXVTI, but now using 7.03 g of dif 1 -inet i J -1 -ethyl propyl) ciciopentadiene (30 mlils), 30 rnoles of tosylate 2- (d) ? met? lam? noet? lo) and 18.7 ml of a 1.6 M solution of butynethium. In the first case, 90% was obtained, and after purification in the 79% column (7.24 grams), of (dirne-tilarninorneti 1) d? (1-rnet? L -1-ethylpropyl) cyclopentadiene. ÍSM Syn esis of (f-dimethylaminoethyl) di-1-methyl-1-1-ethylpropyl) cyclopentadienyl) titanium dichloride The synthesis was carried out as in Example XXXVIII, but now using: 1.53 grams of (dimethylarinyl ethidyl ether-1-ethylpropyl cyclopentadiene) 1.75 grams of ((dimethylaminoethyl) d (1-methyl-ethylpropyl) c? clopentad? dichloride were obtained in? l) ti? .

EXAMPLE XL Preparation of compounds and compounds of alkynyl lithium Preparation of (N. N -di-n-decylaminoetiDtetramethylcyclopentadiene In a three-necked flask, 1.5 g (216 rnilunoles) of Li wire were added to 200 ml of diethyl ether. The solution was cooled to OQC and then 10.0 rnl (98 rni slimes) of 2-bruno-2-benthene were slowly added dropwise. Stirring was continued at room temperature for 30 minutes. The solution turned a greenish-yellow color. Then, the solution was cooled to -25 ° C and 13.05 grams (33.89 ml) of N, N-dL-n-decylainoinyl propionate lo slowly added dropwise with cooling. The temperature rose to 0OC. Then, the reaction mixture was stirred for an additional 5 minutes at room temperature and then 20 rnl of water was added dropwise. The aqueous and ether layers were separated and the aqueous layer was extracted with 2 x 50 mL of diethyl ether. The collected ether layer was dried (MgSO), filtered and concentrated by boiling. The residue was a pale yellow liquid containing 4- (N, N-d? -N ~ dec? Larn-noethyl) -4-hydroxyhepta-2,5-diene, which was characterized by NMR. The performance was .0 grams In a flask of fresh mouths, 10.0 grams of p-toluenesul fonic acid inonohydrate (52.6 inilunoles) were dissolved in 150 rnl of diethyl ether. To this, 15.0 g of the obtained carbinol (32.49 thousand imoles) were added dropwise. Dur-before the dropwise addition, a white suspension formed. Then it was stirred for two hours at room temperature. The solution was neutralized with a Na / C03 solution. The aqueous layers and the area were separated and the aqueous layer was extracted with 2 x 50 ml of diethyl ether. The collected ether layers were dried and the drying agent was removed by filtration. The diethyl ether is then evaporated. The residue contained carbinol (30%) and ligand (70%). Yield: 11 grams of crude product (76%). 5 Grams of this crude mixture was purified by column chromatography to give 3 g of pure ligand. According to this method, the following ligands were synthesized (Cp '= Mß- * Ca; Et - (CHa) a): C 'E + Níet i lo) a: Yield (30%) (Eta) (Me ^) Ca (CHa) aNMßs. : Rendirnien-t o (15%) Cμ'EtNdButiloía: Yield (20%) Cp '(CH (CHß) CHa (et1 lo) a: Yield (30%) Cp'EtN (Me) Pr: Yield (15%) Cp'EtN (n-Bu) s: Yield (50%) Cp'EtN (c? Clohex? Lo) a: Yield (30%) Cμ 'EtN (secBu +? Lo) ß: Yield (15%) Cp' EtN (eti lo) (feni lo): Yield (10%) Cp'EtNf iPropyl) (cyclohexyl): Yield (15%) C? 'EtN (Me) (ethyl): Yield (25%) Cμ'EtN (2- methox? ethyl) 5 > : Yield (25%) EXAMPLE XLl a- Preparation of (N. T.hT-tri? Netil-3, 6-diazahep 1) tetra-methylcyclopentadiene Starting from 2-l? T? O-2-b? Teno and EtOC (0) CHaCHaN (Me) CHa-CH? NM-2, the compound specified in the title was prepared by the method described in the document DE-A-4303647, with a yield of 25%, based on the amount of ester used co or starting material.

Synthesis of n-fN.hr.N / -trimethyl-3,6-diazaheptyl) -2.3.4.5-tet amethylcyclopentad enyl-lydlorothane tanium fTTT) TCaMe * í (CH-,) pN (CHS) (CHK) a ( CHj) 2T i (T11) Cía1 In a Schlenl-flask, 0.21 g (0.838 mmol) of (N, N ', N' -prpnetyl -3,6-d? Azahept 11) tet rarneti 1-cyclopentadiene was dissolved in 15 ml of tetrahydrofuran and then the solution was cooled to -60OC. Then, 0.52 nl of n-b-butyllithium (1.6 M in hexane, 0.832 millirol) was added dropwise. After 2.5 hours, the reaction was stopped and then stirred for 30 minutes at room temperature. In a second Schlenk flask, 15 ml of tetrahydrofuran was added to 0.31 g (0.836 mlles) of Ti (III) Cla.3T? F. Both Schlenl flasks were cooled to -60 ° C and then the organolithium compound was added to the suspension of T (TTI) Cla. After 2 hours, the cooling was stopped and then stirred for 2 hours at room temperature. The solvent was then evaporated. To the residue containing Cl- (N, N ', N'-trrnet.il -3,6-diazaheptyl) -2, 3, 4, 5 -tetrnrnenylcyclopenf ad? Enyl] t? Tan? O (Til) dichloride. 40 pl of petroleum ether were added, which was subsequently evaporated again. The synthesized catalyst was not subjected to additional treatments.

EXAMPLE XLlI a- Preparation of 1- (N-methyl-Nf-dioxolylmethyl) -ethyl) -2.3.4.5-tetramethylcyclopentadienemltitaniof III chloride) CCsMe «(CHa) aN (Me) (H ^ CaH ^ Oa,)) (Ti (IIPCI ^ -I To 0.36 g (1.33 millirnoles) of 1- (N-metii-N- (dioxolylrneti Pet? P-2,3,4,5 -fetrame-t i lcyclopentadiem 1 -lithium, 40 ml of ether was added. of oil in a Schlenk flask: 0.50 g of Ti (III) Cla.3THF (1.35 thousand needles), 30 ml of tet rahydrofuran in a second Schlen flask were added, both Schienk vessels were cooled to -60 ° C. and then the organolithium compound was added to the Ti (ITI) Cla suspension. The reaction mixture was stirred at room temperature for 18 hours and then added to the suspension of T (III). Cl 3 The reaction mixture was stirred at room temperature for 18 hours and then the solvent was evaporated, 50 ml of petroleum ether was added to the residue and then evaporated once more.The residue was a green solid, containing l- ((N-rnet? lN- (d? oxol? lmet? l) et? l) -2,3,4,5-tetrarnethyl cyclopentadienylthiranium III dichloride).

EXAMPLE XLIII to. Preparation d = 1.2.3.4-tetramethyl-5-f 2-cl oroet i 1) c r1n-pentadiene A 1-liter, 1-liter flask, supplied from an addition funnel, a condenser, a mechanical stirrer and a nitrogen inlet, was charged with 30.5 g of 1,2,3,4-tetraineti-1-cyclopentadiene. , 25 moles), dissolved in 700 ml of ethoxyethane and cooled to 2 ° C. Then 160 ml of n-butyllithium (1.6 M in hexane, 0.26 mol) were added dropwise in 2 hours, and then stirred for 18 hours at room temperature with the aid of a mechanical stirrer. . Then, 36.0 g of l-hrorno-2-chloroethane (0.25 rnoles) were added, all at once. The reaction mixture was stirred at room temperature for 10 days. GC analysis of a sample indicated that the conversion of tetramethylcyclopentadiene was 91%. They were added 100 rnl of water to the reaction mixture and then the aqueous phase and the organic phase were separated. The organic layer was washed once with 50 ml of a saturated aqueous solution of sodium chloride, dried (with sodium sulfate), filtered and concentrated by boiling. The residue (43.9 g) was found to have the following composition, according to the gas chromatography (GC) analysis: apart from the starting materials 1-rhizo-2-chloroethane (9% by weight) and 1.2 , 3,4-tetramethylcyclopentadiene (9% by weight), it was only found that non-germanent bound product (84%) and germmalnnent bound product (16%) were present.

S_, Preparation of 4.5.6.7-tetramethyl-esPÍro --- 2.4-l-hf-nta-2.4- The product obtained in section a. (43.9 g), which according to the GC analysis contains approximately 32 g of 1,2, J, 4-tetrarnet? L-5- (2-chloroet? I) c? Clopentadiene (0.175 mol), was dissolved in 300 ml of THF. The solution was cooled to -60 ° C and then 115 ml of n-butyllithium (1.6 M in hexane) was added dropwise.; 0.184 rnoles). The reaction mixture was brought to room temperature and then stirred for 40 hours. The THF was evaporated and the residue was taken up in 200 rnl of ethoxyethane. 100 ml of water was added and then the aqueous phase and the organic phase were separated. The organic phase was washed once with 100 rnl of water. The combined aqueous layers were extracted once with ethoxyethane. The combined organic layers were washed once with 50 mL of a saturated solution of sodium chloride, dried (sodium sulfate), filtered and concentrated to boiling. The residue (43.2 g) was a pale yellow liquid which was purified with the aid of column chromatography (silica gel, petroleum ether as mobile solvent). The yield was 24.2 g of colorless liquid? N which was characterized with the help of ^ H-NMR and by means of GC-MS as 4.5, 6, 7-tetrarnet? L-isoror. - hepta-2, 4- diene. The yield was 93%, based on the amount of 1,2,3,4-f etramet? L-5- (2-chloroetyl) c? Clo? 65% based on 1, 2,3, 4-tetramet? Lc? Clo? Entad? Eno. c. Synthesis dS 1.2.3. -te rametil -5- f 2-. -difeni l fos i noetil) cyclopentadiene In a 100 RN reactor, 3.87 g of di-phenyl phosphine (21 in-l-oles) were dissolved in 25 μL of THF and cooled to 2 ° C. Then, 13.0 nl of n-butyl-11-thio (1.5 M in hexane, 21 mmol) was added dropwise and then stirred for a half hour at 2 ° C. Then, stirring was continued for 1 hour at room temperature. Then, the dark red mixture obtained was cooled to ~60 ° C. To this, 3.08 g of 4,5,6,7-tetramethyl-L-spherical C2.4] -hepta-2,4-diene (21) were added. millimols) as obtained in section b., all at once. The reaction mixture was brought to room temperature and stirred for 3 days. Then, the THF was evaporated.

The residue, a yellow solid, was washed twice with TEQ at OQC. Then, the solid was suspended in 50 ml of ethoxyfen and 5 ml of water was added dropwise. The ether layer and the aqueous layer were separated. The aqueous layer was extracted three times with 25 ml of ethoxyethane. Then, the combined ether layers were concentrated by boiling, whereby 4.72 g of a clear, brown viscous liquid was obtained. Analysis of ^ P-N R and XH-NMR indicated that the residue was 1, 2, 3,4-tetranet-l-5- (2-P, P- d i phenyl phosphoryl) -cyclopentadiene. The yield of 1, 2,3,4-tetrarnet? L-5 ~ (2-P, P-diffene phosphmoet? L) ci clopentadiene, L > roasted in 4,5,6,7-tetra? net? lesp? ro [2.4] -heta-2,4-d? ene, was 67%. After the GC analysis of the product, the purity was found to be > 98%. d. Synthesis d = 1.2.3. -tetramethyl-5- f2-P. P-dimetT 1 osfi no-ethyl) c? Clooentadiene Lithium dunetyl phosphide was prepared by reaction of di-ethyl phenyl phosphite and lithium, hydrolysis with water, distillation of di-ethyl phosphine and reaction of the latter with bufil-lithium (see Ta-shue Chou et al in 3. Org. .__, 4329 (1985)). In a 250 ml reactor, 8.12 g of dirnet 11 lithium phosphide solution in THF (14 rni limoles) were mixed with 25 ml of THF. The obtained solution was cooled to -90SC. To this solution, 1.7 g of 4, 5, 6, 7 ~ tetrarnet? Lesp? RoC2.43-he? Ta- 73 were then added. 2, 4-diene (12 my limóles), obtained as indicated in section b., All at once. The reaction mixture was brought to room temperature and stirred for 2 days and then 20 ml of water was added drop by drop. Then, the THF was evaporated and the residue was extracted with ether (ethoxyethane). The combined ether layers were concentrated to boiling and the residue was distilled in vacuo. The boiling point of the product was 51-52QC (at 0.01 rnrnHg). As indicated by analyzes of 3a-P-NMR and XH-NMR, the distilled product (1.13 g) was mainly 1,2,3,4-tetrainetii-5- (2 -P, P-imet 11 phosphorylate). noet? l) c? clo? entad? eno. The yield of 1,2,3,4-tetrane-t 11-5- (2-P, Pd? Rnet 11 phosph i noet? L) cyclopentadiene based on 4,5,6, .'- tetramet? I- SPLLL ".4l-he? ta-2,4-diene was 46% After GC analysis it was found that the purity was> 95%.

EXAMPLE XLIV to. Preparation dS (1.2.3.4-tetramethylcyclopentadien-5-yl) chloromethyldimethylsilane In a 1500 rnl reactor, 31.0 g of tetraethyclopentephiene diene (0.24 mol) were dissolved in 500 rnl of tetrahydrofuran (THF) and cooled to 2 ° C. Then, 160 rnl was added dropwise. n-butyl (1.6 M in hexane, 0.26 rnoles) and then stirred at room temperature for 18 hours with a mechanical stirrer. The reaction mixture obtained was cooled to -90 ° C. Then 36.3 g of chloromethyiyl ethylsilyl chloride (0.28 rnols) were added all at once. Then, the cooling bath was set aside allowing the reaction mixture to reach room temperature and stirring, in total, for 18 hours. Then 200 rnl of water was added. The THF was evaporated in a rotary evaporator and the residue was extracted 3 times with 200 rnl of ethoxyethane. The combined ether layers were dried over sodium sulfate, the sodium sulfate LO was filtered off and the filtrate was concentrated by boiling. The residue (58.0 g) issues a purity of > 98% (determined by means of gas chromatography (GC)) of (1,2,3, -tetramet? Lc? Clo? Entad? En-5-yl) chlorornet? I ~ dunotyl sil. b. Synthesis of phenyl phenyl phosphino ethyl) f 1.2. .4-tetramethylcyclo-nentadien-5-yl) dimethylsilane .9 g of diphenylphosphine (85 rniliols) were dissolved in 100 rnl of ether. The solution was cooled to 2 ° C and then 53 rnl of n-butyl-1-yl (1.6 M in hexane, 85 millirol) was added dropwise. Once the latter was incorporated, the mixture was stirred for half an hour at 2 ° C and then for 18 hours at room temperature (the dif ferent phosphide of lithium was not completely soluble). Then 100 rnl of THF was added, resulting in a homogeneous solution 00 I'm dark. Then, this solution was added dropwise to a solution of 19.5 g (85 rni limóles) of (1,2,3,4-tef rainet il c? Clopent d? En-5-? L) c romet i Id i met i L si Laño, obtained as described in section a., In 150 rnl of THF at 2QC. The reaction mixture was stirred for 18 hours at room temperature and then the THF was evaporated. 200 ml of oil to the residue, the precipitate was separated by filtration and the filtrate was concentrated to boiling. The residue t ue (diphenyl phosphornethyl) (1,2,3,4-tetrarnetylcyclopentadi en-) ddunethylsilane The yield was 31.8 g.

SL. Synthesis dS (1.2.3.4-tetrap-ethylcyclopentad? En-5-meti 1 i 1) - (N.N-diisonpropylamino) dimethylsilane 1.22 g of dusopropylarnin (12 thousand or so) was dissolved in 25 ml of THF and cooled to 2 ° C. Then, 7.5 ml of n-butyl-thio (1.6 M in hexane) was added dropwise.; 12 my limols) and then stirred for half an hour at room temperature. To the obtained solution, 2.70 g of (1, 2,3, 4-tetrarnet? Lc? Clopentadion-5-yl) chloro? Nephldimethylisilane (12 rnil noles), obtained as described in US Pat. section a. The reaction mixture was stirred at room temperature for 18 hours. The THF was evaporated and 100 ml of ether was added to the residue, after which the formed salts were separated by filtration and the filtrate was concentrated by boiling to obtain 3.0 g of residue. The GC analysis indicated a 100% conversion and a purity of > 90% of (1,2,3,4 -tet rarnet? Lc? Clopentad? En-5-rnet? L?) (N, N-dusopropy l mino) dirnet íl si lño. d. Synthesis of (1.2.3.4-tetramethylcycloPentadien-5-methyl-yl) -fN-N-di-n-butylamino) dimethyl-lane The synthesis described in section c was repeated, the starting materials being 1.75 g (13.5 mmol) of dL-nb? Tilarnin and 3.05 g of (1, 2,3,4-tetrarnet? Lc? clo-? entad? on-5-D-chloroinethyldi ethyl ilane (13.3 rni limol) GC analysis indicated 100% conversion, GC analysis indicated 100% conversion, after concentrating by boiling, 3.95 was obtained. g (Je (1, 2, 3, 4- tetrarneti lciclopentadien- 5-rnet? i? l) (N, N- di-n-butLlar? uno) (irneti lsi l o.

EXAMPLE XLV Synthesis of 1-phenyl phenyl phosphonoethyl dichloride) -? .3. .5- tetramethylcyclopentadieniltitaniofTTT) [CaMe < v (Ch! a) s, PPh12Tl (I? I) Clal In a Schlenk flask, 1.14 g (3,408 rnilunoles) of (di-phenyl-phenyl-noethyl) tetramethylcyclopentad-L-ene were dissolved in 30 rnl of diethyl ether and then the solution was cooled to -60 ° C. Then 2.13 nl of n-butyl-lithium (1.6 M in hexane, 3.41 ml) were added dropwise. The reaction mixture was slowly brought to room temperature and then stirred for 2 hours. In a second Schlenk flask, 40 ml of tetrahydrofuran was added to 1.26 g of Ti (III) Cla.3THF (3.40 rnilirnoles). Both Schlenk flasks were cooled to -60 ° C and then the organolithium compound was added to the suspension of r (III) Cl 3. Then, the reaction mixture was stirred for 60 hours at room temperature, after which the solvent was evaporated. To the residue, 50 in 1 of petroleum ether was added, which was subsequently evaporated to dryness. A green solid containing l- (diphenylphosphinoethyl) -2,3,4,5-tet rarneti L-cyclopenf adienilt-titanium (III) dichloride remained as a residue.

EXAMPLE XLVI T-F-dimethylphosphinoethyl dichloride) -2.3.4.5- tetramethylcyclopentadienyl) titanium (III) rCarie * (CHa) uPMe-, r1 (IT I) C1-2] In a Schlenk mat, 0.78 g (3,709 mmol) of (dimethyl phosphonoyl) tetrarnef-cyclopentadiene were dissolved in 30 ml of diethyl ether and then the solution was cooled to -60 ° C. Then, 2.32 nrn of n-butyllithium (1.6 M in hexane, 3.71 mmol) was added dropwise. The reaction mixture was brought slowly to room temperature and then stirred for 2 hours. A white suspension was formed. In a second Schlenl-- flask, 40 rnl of tet rahydrofuran was added to 1.37 g of Ti (IIT) Cla.3THF (3.70 thousand imols). Both Schlenl- 'flasks were cooled to -60 ° C and then the organolithium compound was added to the Ti (III) Cla suspension. Then, the reaction mixture was stirred for 60 hours at room temperature, after which the solvent was evaporated. To the residue, 50 rnl of petroleum ether was added, which was subsequently evaporated to dryness. A green solid containing l- (dirnethylphosphinoephyl) -2,3, 4,5-tetr-amet? Lc? Clopentad? In dichloride (III) dichloride remained as residue.

EXAMPLE XLVII Synthesis of Cl-f dichloride 2-diphenylphosphino-l-s? La-l. 1 -d? Methyl) et l > -2.3.4.5-tetramethylc? CloPentad? In? L - titanium (III) v Cl-Tf 2-diphenylphosphino-l-sila-l. 1-dimethyl) et? LT - 2.3.4.5- tetra ethylcyclopentadienyl-ldimethyl-tiltioflIT) rcaMe * (Si (CH3) ZCH2) PPhsT? (III) Cl] and rcaMe * (Si (CH3)., CH2) PPh ^ Ti (III) Me ^ l To 1.57 g (4.15 rniliinoles) of. { (2-d? Phen? L fos? No-l? S? La ~ l, d-met? L) eti l} ] tetrarneti lcyclopentadiene, dissolved in ml of diethyl ether, 8.3 rnl of lithium hard diisopr-opylaini (0.5 M in diethyl ether, 4.15 milli mol) were added at -78 ° C. After 18 hours of stirring at room temperature, it had formed a cloudy orange yellow solution. The diethyl ether evaporated and the residue was washed twice with oil. After having concentrated it thoroughly, there remained, as a residue, 1.41 g of a pale yellow crystalline product which it contained. { (2-di ten il fos fines- 1 -si 1 al, 1- dimet 11) ef ilMetrarnetil-ci clopent a (jieni 1-1 Lt. o The organolite compound LO was dissolved in 20 ml of tet rah Then, the orange yellow solution, at -78 ° C, was added to 1.36 g (3.76 milliliters) of water.

TL (1II) C1 =,. 3THF. Then, the reaction mixture was stirred for 3 hours in the cold bath and then for 18 hours at room temperature. A dark green solution had now formed, which was concentrated by boiling and washed twice with 10 rnl of petroleum ether. Now there remained, as residue, 1.5 g of a green solid containing dichloride of 1 -. { (2 di fonil fosf ino- 1- si La-l, 1-d? Rnet? 1) et? 1 } ~ 2, 3,4,5-tetrarnetylcyclopenf adiem 1 Ititanium TTI). To 0.534 g (1.08 my limols) of [I- dichloride]. { (2-di f em 1 fos f L no- 1 - e i la - 1, 1 - di metí 1) e? L} -2, 3,4,5-tetramethylcyclopentadienylthione (ITI), lithium chloride], 20 ml of diethyl ether were added and then, at -70 ° C., 1.35 ml of rethyllithium (1.degree. , 6 M in hexane, 2.16 inylinols). After 2 hours of stirring at room temperature, the solvent was removed and the residue dried during 2 hours in vacuum. Then 20 rnl of petroleum ether was added to the product and then filtered. The filtrate was concentrated to boiling and then dried for 18 hours in vacuo. There remained, as residue, 0.42 g of brownish black oil containing Cl ~. { (2-d? Femifosfi no-1-sil a-l, l-dirnet? I) et i l} ~ 2,3,4,5-tetrarnet? Lc? Clo? Entad? In? L üdirpetiiti amo (TTT).

E.1FMPLO XLVIII Synthesis of dichloride d £ Cl-f f 2-d? Methylphosphino-l-l-1,1-dimethyl) ethyl1--2.3.4.5-tetramethylcyclopentadienyl-litannof TTT) I "Cs e (Sl (CH3) .¿-CHE») PMe2 Ti (111) C l21 To 0.88 g (4.42 ml) (je. {- (2 ~ d? -ethyl fos-fine-1 -s? La-1, 1-d? Rnet? L) et? L.}. tetrarnet? lc? clopentadiene, dissolved in 25 rnl of diethyl ether, 8.8 rnl of lithium hard dusopropylamine (0.5 M in diethyl ether, 4.42 r ilirnoles) was added at -78 ° C. After 18 hours of agitation at ambient temperature, a pale, clear yellow solution was formed. The diethyl ether was evaporated. After concentrating well by boiling, 1.14 g of yellow oil containing C (2-d? Methyphosphino-ls? La-1, 1-dirnethyl) et? L) te rrnethylcyclopentadie remained as a residue. i 1 -11 uncle. The organolithium compound was dissolved in 20 ml of tetrahydrofuran. Then the yellowish orange solution, at -78 ° C, was added to 1.36 g (3.76 rnilirols) of Ti (III) Cla.3THF. Then, the reaction mixture was stirred 06 for 3 hours in the cold bath and then for 13 hours at room temperature. Now a dark green solution had formed, which was concentrated by boiling and washed twice with 10 ml of petroleum ether. Now 1.5 g of a green solid containing Cl- dichloride remained. { 2-di me ti 1 fos f i no- 1 - si 1 a - 1, 1 d irneti 1) eti 1.}. - 2,3,4,5-fef r-amet? Lc? Clo? Entad? In? Pt? Tan? O (III). 1.13 g (4.41 mmol) of the organo-lithium compound were dissolved in 30 ml of tetrahydrofuran and cooled to -78 ° C. This was then added to a cold suspension of 1.67 g (4.5 rni limole) of TifITI) C1.3THF in 25 ml of cold phase and then stirred for 3 hours at room temperature. The brownish green suspension was concentrated by boiling and washed twice with petroleum ether. Finally, there remained, as residue, 730 rng of a dark green precipitate containing C 1 - - (2-dimethophosphine-1-si-1, 1-dirnethyl) et 11 dichloride} - 2, 3, 4, 5 -tet raineti lciclopentadie ill t.L an? O (III).

EXAMPLE XLIX Synthesis of Cl-f dichloride 12-dibutylamino-2-s? La-2.2-dimethyl) ethylT-2.3.4.5-tetramethylcycl? Pentad? Enyl-litannofTTT) l-CMe * (CHsS.? (CH3) aN (nC * H «,) 2T? (111) Cla] 1.39 g (4.33 rmlirnoles) of [(2-d? B? T? Ia? N? No-2-s? La-2,2-d? Rne? L) et? L was dissolved} Tetranet? lc? clopentadiene in 25 ml of diethyl ether and then, at -78 ° C., 9.0 ml of hard dibutyl lithium (0.5 M in diethyl ether, 4.5 mmol) were added. This reaction mixture was stirred for 18 hours, after which a cloudy yellow suspension had formed. The solvent was separated and then washed with petroleum ether for a certain number of times. After concentrating completely by boiling, a yellowish brown oil containing 1- was left as residue. { (2 - di but i -1 arní no - 2 - si la - 2, 2 - d irneti 1) et 11} - 2, 3,, 5 ~ tef ra ethylcyclopentadieni lo. 4.33 rnilirols of the organolipium compound thus obtained were dissolved in 25 rnl of tetrahydroturan and, at -70QC, were added to 1.95 g (5.26 rnilirnols) of T (III) Cla.3THF in 25 rnl of tetrahydrofuran . After 3 hours of stirring at room temperature, the greenish brown solution was completely concentrated by ebition and washed twice with 10 ml of petroleum ether. 1.5 g of a reddish brown oil containing 1 ~ dichloride remained. { (2 -d? But? Ia? N? No-2-s? La-2,2-dirnetjDetii] -2, 3,4, 5-te ra til ci clopent diemlti tamo (III).

Polymerization experiments I - I A. The copolymeation of ethylene with propylene was carried out in the following manner. A 1-liter stainless steel reactor was charged, in dry Na, with 400 ml of pentamethiheptane (PMH) and 30 mrnolee of tertiary aluminum (TEA) or trioctylaluminum (TOA) as a purifying agent. The reactor was pressurized at 0.9 MPa with purified monomers and conditioned in such a way that the ratio of propylene retylene in the gas above the PMH was 1: 1. The content of the reactor was brought to the desired temperature while it was being stirred. After the conditioning of the reactor, the metal complex (5 rnrnol.es) to be used as a catalyst and the cocatalyst (30 mol of BFa.0) and previously mixed over a period of 1 minute were loaded. in the reactor by means of a pump. The mixture was pre-mixed in approximately 25 ml of PMH in a vessel to provide the catalyst and a subsequent wash was carried out with approximately 75 rnl of PMH, always under a stream of 2 dry. During the polymerization, the rnonornero concentrations were kept constant to the extent possible by supplying the reactor with propylene (125 liters Cs.t.p / hour) and ethylene (125 liters Es.t.p.1 / hour). The reaction was monitored on the basis of the temperature trend and the progress of the incorporation of rnonornero. After 10 minutes of polymerization, the monomer feed was stopped and the solution was pressure removed from the reactor and collected. The polymer was dried under vacuum for 16 hours at about 120 ° C. B. Ovenpolymerization of ethylene and copolymerization of ethylene with octene were carried out in the following manner. 600 ml of a mixture of alkanes (pentane and heptane or solvent with a special boiling point) were introduced into the reaction medium, in dry N, in a stainless steel reactor with a volume of 1.5 liters. Then, the desired amount of dry ocphene was introduced into the reactor (therefore, this amount can also be zero). Then, the r-eactor, with stirring, is heated to the desired temperature at a desired ethylene pressure. In a container for providing catalyst, with a volume of 100 ml, 25 rnl of the mixture of alkanes co or solvent were incorporated. Here, the desired amount of a cocatalyst containing Al was previously mixed over a period of 1 minute with the desired amount of metal complex, such that the ratio of Al / (me in the complex) to the mixture of reaction is equal to 2000. Then, this mixture was incorporated into the reactor and then the polymerization started. Thus, the polymerization reaction initiated was carried out isothermally. The ethylene pressure was kept constant at the established pressure. After the desired reaction time had elapsed, the ethylene supply was stopped and the reaction mixture was removed from the reactor and the reaction was stopped by the addition of methanol. The reaction mixture containing rnetanol was washed with water and HCl, in order to remove catalyst residues.

Then, the mixture was neutralized with NaHCO 3, after which the organic fraction was mixed with an antioxidant (Irganox 1076, registered mark) in order to stabilize the polymer. The polymer was dried under vacuum (for 24 hours at 70 ° C). In both cases, the following conditions were modified: metallic type complex and amount of scavenging agent-type and quantity of temperature co-catalyst Actual conditions are those expressed in Table T.

I-1 or u.

Table I BF20: tetrakis (pentafluorophenyl) borate MAO: methylaluminoxane, by Hitco

Claims (9)

NOVELTY OF THE INVENTION CLAIMS

1. - Compound containing polysubstituted cyclopentadiene, at least one of whose substituents is the for-rna -RDR'r-, where R is a linkage group between the cyclopentadiene and the group DR '", is a heteroatom selected from group 15 or 16 of the Periodic Table of the Elements, R 'is a substituent and n is the number of R' groups attached to D, with the exclusion of compounds containing cyclopentadiene in which: there are 2 adjacent methyl groups at the same time co or Substituted in combination with a group of the form -RDR ', -,., in which the Rnetylene group and DR'r, is a dimethylamine group; there are 4 methyl groups at the same time as a substituent on combination with a group of the form -RDR'r ,, in which R is an ethylene or propylene group and DR'n is a diphenylphosphinyl group; there are 4 methyl groups at the same time as a substituent in combination with a group of the form -RDR'n / wherein R is a di-ethylsilylene group and DR'n is an ethoxy group; there is a tere -butyl group at the same time as a substantive in combination with a group of the form -RDR'n / in which R is an ethylene group and DR'n is a rnetoxy group; there are 4 methyl or ethyl groups at the same time as a binder in combination with a group of the forrna-RDR'n, wherein R is a rnetylene or ethylene group, D is 0, N or S and R 'is methyl.

2. - Compound according to claim 1, wherein the group R has the structure (-ER3? -) p in which p = 1-4, E is an element of group 14 of the Periodic System of the Elements and in which the groups Rs are in each case, separately, H or a hydrocarbyl radical,

3. Compound according to claim 2, wherein D is selected from the group consisting of N, 0, P and S.

4. Compound according to any one of claims 1-3, wherein D is nitrogen.

5. Metallic complex comprising metal of group 4-10 of the Periodic System of the Elements and expensive earths, in which a compound according to any one of claims 1 to 4 is present as a ligand. 6.- Metal complex , in which the metal is not present in its highest state of valence and in which it is present, as a ligand, only a compound containing polysubstituted cyclopentadiene, at least one of its constituents is of the form RDR'n, in which R is a linkage group between cyclopentadiene and the group DR'r- ,, D is a hetero-atom selected from group 15 or 16 of the Periodic Table of the Elements, R 'is a substituent and n is the number of groups R 'linked to D. 7. Metallic complex according to claim 6, in which the metal is selected from the group consisting of Ti, Zr, Hf, V and Cr. 8. Use of a metal complex according to Claim 5-7, co or a catalytic component. 9. Use according to claim 8 for polyarylene r-olefins.