MXPA97004116A - Improved preparation complexes of titanium (ii) ocirconio ( - Google Patents

Abstract

The present invention relates to a process for preparing a metal complex containing one and only one delocalised, cyclic, linked II-group, said complex corresponding to the formula: wherein M is titanium or zirconium in the formal oxidation state +2; L is a group containing an anionic, delocalized, cyclic II-system, through which the group joins M and whose group is also joined to Z; Z is a portion linked to M via an o-ligation, comprising boron, or a member of Group 14 of the Periodic Table of the elements and also comprising nitrogen, phosphorus, sulfur or oxygen, said portion having up to 60 atoms that are not hydrogen; X is a neutral conjugated diene, optionally substituted with one or more groups hydrocarbyl, said Z having up to 40 carbon atoms and forming a II-complex with M; X'is a neutral Lewis base ligand selected from amines, phosphines and ethers, said X having from 3 to 20 atoms without hydrogen; from 0 to 3, said process comprising contacting a metal halide compound according to the formula: wherein, M * is titanium or zirconium in the formal oxidation state +3; M ** is titanium or zirconium in the formal oxidation state +4, X * is halide, and L, Z, Z'y n are as previously defined, with a free diene corresponding to X, and subsequently or simultaneously contacting the resulting reaction mixture with a derivative Grignard of a C1-20 n-alkane to form the desired metal complex

Description

IMPROVED PREPARATION OF TITANIUM (II) OR CIRCUMIUM MI COMPLEXES This invention relates to a process for preparing certain titanium and zirconium complexes comprising a single, delocalized, cyclic p-linked ligand group, wherein the metal of said complexes is the formal oxidation state +2. More particularly, this invention relates to such processes wherein the metal is covalently linked to the cyclic group via the delocalized p-system and also covalently linked thereto via a divalent ligand group. Said complexes are referred to herein also covalently linked thereto via a divalent ligand group. Said complexes are referred to in the art as complexes of "restricted geometry". The preparation and characterization of certain complexes of zirconium bisciclopentadienil and diene of hafnium are described in the following references: Yasuda, et al., Organometallics, 1, 388 (1982) (Yasuda I); Yasuda, and others, Acc. Chem. Res. 18, 120 (1985), / Yasuda II); Erker and others, Adv. Organomet. Chem. , 24, 1 (1985); and US-A-5, 198,401. The preparation of certain monocyclopentadienyl diene complexes of Ti, Zr and Hf, lacking the present bridged ligand structure, was described in Yamamoto et al., Organometallics, 8, 105 (1989) (Yamamoto) and Blenkers, J. and others, Organometallics, 6. 459 (1987).

Metal complexes of restricted geometry, including titanium complexes and method for their preparation, are described in EP-A-416,815; EP-A-468,651; EP-A-514,828; EP-A-520,732 and WO93 / 19104, as well as US-A-5,055,438, US-A-5,057,475; US-A-5,096,867, US-A-5,064,802 and US-A-132,380. According to one embodiment of the present invention, there is provided a process for preparing a metal complex containing one and only one delocalised, cyclic p-linked group, said complex corresponding to the formula: Z X'n L M - X wherein M is titanium or zirconium in the formal oxidation state +2; L is a group that contains an anionic, delocalized, cyclical ü-system, through which the group joins M and whose group is also linked to Z; Z is a portion linked to M via a s-ligation, comprising boron, or a member of Group 14 of the Periodic Table of the Elements and also comprising nitrogen, phosphorus, sulfur or oxygen, said portion having up to 60 non-hydrogen atoms; X is a neutral conjugated diene, optionally substituted with one or more hydrocarbyl groups, said Z having up to 40 carbon atoms and forming a p-complex with M; X 'is a neutral Lewis base ligand selected from amines, phosphines and ethers, said X' having from 3 to 20 atoms without hydrogen; and n is a number from 0 to 3; said process comprising contacting a metal halide compound according to the formula X'r Z X'n - M ** - X * 2 L M * - X * wherein, M * is titanium or zirconium in the formal +3 oxidation state; M ** is titanium or zirconium in the formal oxidation state +4; X * is halide; and L, Z, Z 'and n are as previously defined; with a free diene corresponding to X, and subsequently or simultaneously contacting the resulting reaction mixture with a Grignard derivative of a C, .2 n-alkane to form the desired metal complex. According to a second embodiment of the present invention, there is also provided a process for first preparing the above starting cyclic complexes in situ. Therefore, a process for preparing a metal complex containing one and only one cyclic group is provided. unlocalized, said complex corresponding to the formula: Z X'n M - X wherein, M is titanium or zirconium in the formal oxidation state +2; L is a group that contains an anionic, delocalized cyclic fl-system, through which the group is bound to M and whose group also joins Z; Z is a portion linked to M via a s-ligature, comprising boron, or a member of Group 14 of the Periodic Table of the elements, and also comprising nitrogen, phosphorus, sulfur or oxygen, said portion having up to 60 atoms that are not hydrogen; X is a conjugated neutral diene, optionally substituted with one or more hydrocarbyl groups, said x having up to 40 carbon atoms and forming a p-complex with M; X 'is a neutral Lewis base ligand of amines, phosphines and ethers, said X' having from 3 to 20 atoms that are not hydrogen; and n is a number from 0 to 3; said process comprising; 1) contacting a metal halide compound according to the formula M * (X *) 3X'no M ** (X *) 4X'no M ** (X *) 4X'n, where M * is titanium or zirconium in the formal oxidation state +3; M ** is titanium or zirconium in the formal oxidation state +4; and X * is halide; with a dianion salt corresponding to the formula: M * LZ, where: M 'is a Group 1 metal, MgCl or MgBr or two groups together are a Group 2 metal; to form a complex of intermediate metals according to the formula X'n XV. M ** - x *., - M * -X * where L, Z, M **, X *, X ', M * and n are as previously defined; 2) when the metal in said intermediate metal complex is in the formal +3 oxidation state, it is optionally contacted with an intermediate metal complex with an oxidant to form an intermediate metal complex according to the formula: X 'r \ X * 2 where L, Z, M **, X *, X' and n are as previously defined; and 3) contacting the intermediate metal complex with a free diene corresponding to X and subsequently or simultaneously contacting the resulting reaction mixture with a Grignard derivative of a C-20 n-alkane to form the complex of desired metals. Any reference to the Periodic Table of the Elements herein must refer to the Periodic Table of the Elements published and copyrighted by CRC Press, Inc., 1989. Also, any reference to a Group or Groups must be made to the Group. o Groups as reflected in this Periodic Table of the elements using the IUPAC system to number groups. The diene X group does not decompose under the reaction conditions used to prepare the complexes of the invention. Under subsequent polymerization conditions or in the formation of catalytic derivatives of the present complexes, the diene group, X, can withstand chemical reactions or be replaced by another ligand. The titanium and zirconium complexes present contain a neutral diene ligand which is coordinated via p-complex formation through the diene double bonds and not through the metalacycle containing s-ligatures (s-ligation diene) in where the metal is in the formal oxidation state +4. Said distinction is easily determined by X-ray crystallography or by NMR spectral characterization according to the techniques of Yasuda I, Yasuda II and Erker, and others, Supra, as well as the references cited therein. By the term "p-complex" is meant both the donation and re-acceptance of the electron density by the ligand p-ligand orbitals are obtained, ie, the diene is p-linked (p-linked diene). A suitable method for determining the existence of a p-complex in conjugated diene containing metal complexes is the measurement of atomic metal-carbon separations for the carbons of the conjugated diene using common X-ray crystal analysis techniques. Measurements can be made of atomic separations between the metal and C1, C2, C3, C4 (M-C1, M-C2, M-C3, M-C4, respectively) (where C1 and C4 are terminal carbons of the conjugated diene group). of 4 carbons and C2 and C3 are internal carbons of the conjugated diene group of 4 carbons) and C2 and C3 are the internal carbons of the conjugated diene group of 4 carbons). If the difference between these junction distances,? D. using the following formula: is greater than -0.15A, the diene is considered to form a p-complex with M. In the use of said X-ray crystal analysis techniques, at least "good" and preferably "excellent" determination quality is used. as defined by G. Stout et al., X-ray Structure Determination, A Practical Guide. Macmillan Co., pg 430-431 (1968). Examples where the above method for the determination of p-complexes has been applied to the prior art are found in Erker, et al., Angew. Chem. Int. Ed. Eng., 23, 455-456 (1984) (Erker et al.) And Yamamoto, Supra. In the above reference (? 3-allyl) (? 4-butadiene) (? S-cyclopentadienyl) zirconium was characterized crystallographically. The distances of M-C1 and M-C4 were both of (± 0.005) Á. The distances M-C2 and M-C3 were both of 2,463 (0.005) A, giving a? d of -0.103 A. In the last reference, it was shown that the (? 5-pentame thylcyclopentadienyl) (? 4-1,4-diphenyl-1,3-butadiene) titanium chloride having distances M -C1 and M-C4 of 2.233 (± 0.006) A. The distances of M-C2 and M-C3 were both of 2.293 (± 0.005) A, giving a? D of -0.060 A. Erker and others also described bis (cyclopentadienyl) zirconium (2,3-dimethyl-1,3-butadiene). In this complex the distances of M-C1 and M-C4 were 2,300 A. The distances of M-C2 and M-C3 were both of 2.597 A, giving a? D of -0.297 A. Consequently, this complex contains a diene s-joined and the zirconium is in the formal +4 oxidation state. Alternatively, the complexes of the present invention wherein X is a conjugated diene in the form of a p-complex and M is in the formal oxidation state +2 are identified using nuclear magnetic resonance spectroscopy techniques. The teachings of Erker, and others, Supra. C. Kruger, et al., Organometallics, 4, 215-223, (1985), and Yasuda I, Supra, describe these well known techniques for distinguishing between p-linked complexes and metallocyclic coordination or s-linked diene complexes. The reactions of this invention can be carried out at temperatures of -100 ° C to 300 ° C, preferably 0 to 80 ° C. The reaction medium suitable for the formation of the complexes are hydrocarbons and halo, hydrocarbons, ethers and cyclic, aliphatic and aromatic ethers. Examples include branched chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane and mixtures thereof, cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; hydrocarbyl substituted aromatic and aromatic compounds such as benzene, toluene, xylene, and styrene, alkyl ethers having from 1 to 4 carbons in each alkyl group; C1.4 dialkyl ether derivatives of polyalkylene glycols, and tetrahydrofuran. Mixtures of the above are also suitable. The process generates the desired metal complex in high yields and efficiencies due to the fact that the n-alkyl Grignard reagent is much more efficient in the conversion of the halide precursors which are secondary or tertiary alkyl Grignard reagents. Without wishing to be bound by any particular theory, it is thought that in the presence of the conjugated diene reagent, a Group 4 metal complex was formed by the reaction of the precursor metal halide with the n-alkyl Grignard reagent which is reduced to oxidation state +2 in situ. Therefore, the process achieves high yields of the desired complex where the Group 4 metal is in the formal +2 oxidation state without the addition of conventional reducing agents, such as Group 1 or 2 metal amalgams such as Hg / Na or K / Na. Furthermore, in a preferred embodiment, the reaction is carried out in an aprotic polar solvent, especially an aliphatic ether, more preferably diethyl ether, tetrahydrofuran (THF) or dimethoxyethane (DME). In such solvents, the Grignard reagent is relatively soluble. This allows the use of non-polar solvents, especially hydrocarbons, in which the Grignard reagents and metal by-products are relatively insoluble, to be used in order to recover the desired reaction product. All steps of the reaction can be performed in sequence in a single reactor vessel without isolating the intermediates, thus greatly assisting the large-scale commercial practice of the process. The recovery process usually involves the separation of the resulting salt byproducts and the unreacted Grignard reagent and the devolatilization of the reaction medium. As previously mentioned, extraction in a secondary solvent, especially an alkane, is highly convenient. The relative amounts of the respective reactants are not critical to the process, but stoichiometric amounts are generally employed for the most economical operation. Specifically, the amount of Grignard reagent used is convenient in a molar ratio of 1: 1 to 3: 1 compared to the amount of intermediate metal halide. The amount of diene reagent used is convenient in a molar ratio of 1: 1 to 30: 1, preferably in a molar ratio of 1: 1 to 10: 1, compared to the amount of intermediate metal complex. Preferred neutral Lewis bases include pyridine, diethyl ether, tetrahydrofuran (THF), 1,2-dimethoxyethane (DME) or tetramethylethylenediamine (TMEDA). The Grignard complex (either the derivative of -LZ- or the n-alkane) can also be in the form of an auxiliary, such as the Grignard auxiliary coordinated with DME or THF.

In the optional oxidation step performed in the alternative embodiment of the invention, any suitable oxidant may be employed. Preferred oxidants are C? -? Or halogenated organic compounds, such as 1,2-dichloroethane, methylene chloride or chloroform, which are only subjected to electron oxidations by incorporating only the halide group in the metal complex. The use of said halogenated organic oxidants in this form is further described in EP-A-514,828.

As far as the complexes can only make up a p-linked, anionic, cyclical delocalized group, it follows that Z or X. alone or in combination, can not comprise a cyclopentadienyl group or another delocalized cyclic p-linked group. The preferred metal coordination complexes according to the present invention correspond to the formula: / \ CD M - X wherein Z, M and X are as previously defined, and Cp is a group of C5H4 bonded to Z and attached to a? 5 to M binding mode or is such that a group attached? 5 substituted with one to four substituents independently selected from hydrocarbyl silyl, germyl, halo, cyano and combinations thereof, said substituent having up to 20 non-hydrogen atoms and, optionally, one or two pairs of said substituents together form a hydrocarbylene group of C2-? or, thus causing that Cp have a fused ring structure. The coordination complexes prepared according to the present invention correspond to the formula: wherein: R 'each time it is presented, is independently selected from hydrogen, hydrocarbyl, silyl, germyl, halo, cyano and combinations thereof, said R' having up to 20 non-hydrogen atoms, and optionally, one or two pairs of said substituents each form a hydrocarbylene group of C2-? or, thereby causing Cp to have a fused ring structure; X is a conjugated diene group,? 4-attached neutral, having up to 30 non-hydrogen atoms, which forms a p-complexes with M; Y is -0 -, - S-, -NR * -, -PR * -; M is titanium or zirconium in the formal oxidation state +2; Z * is SiR * 2, CR * 2, SiR * 2 SiR * 2, CR * 2 CR * 2, CR * = CR *, CR * 2 SiR * 2, or GeR * 2; wherein: R * each time it occurs is independently hydrogen or a selected member of hydrocarbyl, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said R * having up to 10 non-hydrogen atoms. Preferably, R 'independently each time it occurs is hydrogen, hydrocarbyl, silyl, halo or a combination thereof, said R' having up to 10 non-hydrogen atoms, or one or two pairs of adjacent R 'substituents form together a hydrocarbylene group of C2-? 0, thus causing Cp to have a fused ring structure. More preferably, R 'is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, (including where all isomers are), cyclopentyl, cylcohexyl, norbornyl, benzyl or phenyl or one or two adjacent pairs of substituents R' together they cause the entire C5R'4 group to be an indenyl, tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl or octahydrofluorenyl group. Preferably, in addition, at least one of R 'or R * is an electron donor moiety. By the term "electron donor" is meant that the portion is more electron donor than hydrogen. Therefore, Y is highly preferable in a group containing nitrogen or phosphorus corresponding to the formula -N (R ") - or -P (R") -, where R "is hydrocarbyl of C1.10 Examples of groups X suitable include: 4-1, 3-pentanediene, -2,4-hexanediene,? -1,4-di-phe nyl-1,3-buta-diene;, -3-methyl-1,3-pentanediene; 4-1,4-dibenzyl-1,3-butanediene; 4-1,4-ditolyl-1,3-butanediene; 4-1,4-bis (trimethylsilyl) -1,3-butadiene; -1- (3-methylphenyl) -4-phenyl-1,3-butanediene;? 4-1- (4-t-butylphenyl) -4-phenyl-1,3-butanediene;? 4-1- (3- methylphenyl) -4-phenyl-1,3-butanediene, and 4-1- (3-methoxyphenyl) -4-phenyl-1,3-butanediene The most highly preferred metal coordination complexes prepared according to the present invention invention with amidosilane- or amidoalkanediyl- compounds corresponding to the formula wherein: M is titanium; X is? -1, 3-pentanediene, 4-2.4-hexadiene; 4-1,4-diphenyl enyl-1,3-butadiene; ? -3-methyl-1,3-pentanediene; 4-1, 4-dibenzyme.3-butanediene; 4-1,4-ditolyl-1,3-butanediene;; 4-1, 4-bis (trimethylsilyl) -1,3-butadiene; R 'is hydrogen or methyl or one or two pairs of R' groups together cause the ring structure to be an indenyl group. tetrahydroindenyl, fluorenyl or octahydrofluorenyl; R "is hydrocarbyl of C? -? 0; R" 'is independently in each presentation hydrogen or hydrocarbyl of d.10; E is independently whenever silicone or carbon is present; and m is 1 or 2. Examples of the most highly preferred metal complexes prepared in accordance with the present invention include compounds wherein R "is methyl, ethyl, propyl, butyl, pentyl. hexyl, (including all isomers of the above where applicable), cyclododecyl, norbornyl, benzyl, or phenyl; (ER '"2) m is dimethylsilane, or ethanediyl, and the cyclic delocalized p-linked group is cyclopentadienyl, tetramethylcyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl or octahydrofluorenyl.The highly preferred diene compounds are: 1,3- pentadiene, 2,4-hexadiene, 1,4-diphenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 1,4-dibenzyl-1,3-butadiene, 1,4-ditolyl-1, 3-butadiene; 1,4-bistrimethylsilyl) -1,3-butadiene; 1- (4-t-buitylphenyl) -4-phenyl-1,3-butadiene; 1- (3-methylphenyl) -4-phenyl-1 , 3- butadiene and 1- (3-methoxyphenyl) -4-phenyl-1,3-butadiene All positional and geometric isomers of the above diene reagents can be used The complexes become catalytically active by combination with a cocatalyst of activation or by the use of an activation technique Activation cocatalysts suitable for use herein include polymeric or oligomeric alumoxanes, especially methylalumoxane, methylalumo xano modified by aluminum of tri-isobutyl, or alumoxane of di-isobutyl; strong Lewis acids, such as, Group 13 compounds substituted with C? .30 hydrocarbyl, especially tri (hydrocarbyl) aluminum- or tri (hydrocarbyl) boron compound and halogenated derivatives thereof, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially perfluorinated tri (aryl) boron compounds, and more especially tris (pentafluorophenyl) borane; non-polymeric, inert, compatible, noncoordinating ion formation compounds (including the use of said compounds under oxidation conditions); Volume electrolysis and combinations of cocatalysts and activation techniques. The cocatalysts and activation techniques above have been previously taught with respect to different metal complexes in the following references: EP-A-277,003, US-A-5, 153,157, US-A-5,064,802. EP-A-468,651 (equivalent to US Series No. 07 / 547,718), EP-A-520,732 (equivalent to US Series No. 07 / 876,268), EP-A-520,732 (equivalent to US Series Nos. 07 / 884,966 filed May 1, 1992) and US-A-5,372,682, the teachings of which are incorporated herein by reference. Strong Lewis acid combinations, especially the combination of a trialkylaluminum compound having from 1 to 4 carbons in each alkyl group and a tri (hydrocarbyl) boron compound having from 1 to 10 carbons in each hydrocarbyl group, especially tris ( pentafluorophenyl) borane, further combinations of said strong Lewis acid mixtures with a polymeric or oligomeric alumoxane and combinations of a single strong Lewis acid, especially tris (pentafluorophenyl) borane with a polymeric or oligomeric alumoxane, are especially desirable activating cocatalysts.

The catalysts are suitably employed in the polymerization of olefins according to the known Ziegler-Natta polymerization conditions. Especially suitable are polymerization temperatures of 0-250 ° C and pressures of atmospheric to 1000 atmospheres. They can be used if desired, conditions of suspension process, solution, slurry, gas phase or others. A support can be used, especially silica, modified silica (silica modified by calcination, treatment with a trialkylamino compound having 1 to 10 carbons in each alkyl group or treatment with an alkylaumoxane), alumina or a polymer (especially polytetrafluoroethylene or a polyolefin) and is conveniently employed when catalysts are used in a gas phase or slurry polymerization process. The support is preferably employed in an amount to provide a weight ratio of catalyst (based on metal): support from 1: 1000,000 to 1:10, more preferably from 1: 50,000 to 1:20 and even more preferably from 1 : 10,000 to 1:30. In most polymerization reactions, the molar ratio of catalyst: polymerizable compounds employed is 10"12: 1 to 10" 1: 1, more preferably 10"12: 1 to 10: 5: 1. for solution polymerizations are non-coordinating inert liquids Examples include straight or branched chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane and mixtures of the same cyclic or alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcyclohepane , and mixtures thereof; perfluorinated hydrocarbons such as C4-10 perfluorinated alkanes, and alkyl-substituted aromatic and aromatic compounds such as benzene, toluene and xylene. Suitable solvents also include liquid olefins which can act as monomers or comonomers including ethylene, propylene, 1-butene, butadiene, cyclopentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1, 4 -hexadiene, 1-octene, 1-decene, styrene, divinylbenzene, alkylbenzene, vinyltoluene (including all isomers alone or mixed), 4-vinylcyclohexene and vinylcyclohexane. Mixtures of the above are also suitable. The experts will appreciate that the invention described herein may be practiced in the absence of any component that has not been specifically described. Having written the invention, the following examples are provided as an additional illustration thereof and should not be construed as limiting. Unless stated otherwise, all parts and percentages are expressed on a weight basis. Example 1 Preparation of 1,3-pentadiene of (t-butylamino) (tetramethyl-? 5-cyclopentadienyl) dimethylsilantitanium A. from (t-butylamino) (tetramethyl-? -cyclopentadienyl) dimethylsilantitanium chloride and n-BuMgCI in DME heated to reflux In a glovebox under inert atmosphere, 0.25 g (0.68 mmoles) of C5Me4SMeMeNCMe3TiCI2 ((t-butylamido) (tetramethyl-? s-cyclopentadienyl) dimethylsilanetitanium chloride) was dissolved in 20 ml of 1, 2-dimethoxyethane (DME). To this solution were added 0.34 ml (3.39 mmol) of 1,3-pentadiene followed by 1.02 ml of 2M n-uMgCI in diethyl ether (2.04 mmol). The color of the mixture changed to a dark brown color. The reaction mixture was refluxed for one hour, then cooled to room temperature (20 ° C) and the volatile materials were removed under reduced pressure. The solid residue was extracted with pentane and the extract was filtered. The pentane was removed under reduced pressure leaving purple / black microcrystals of the desired product (Formula A). which was identified by the 1H NMR analysis. The yield was 0.21 g, 84 percent.

B. from (t-butylamido) (tetramethyl-? -cyclopentadienyl) dimethylsilantitanium dihydrochloride and n-BuMgCI in DME at 40 ° C. The reaction conditions of Example 1A were substantially repeated except that 0.50 g (1.36 mmoles) of C5Me4SiMe2NCMe3TiCl2, 25 ml of DME, 0.68 ml (6.79 mmol) of 1,3-pentadiene and 2.04 of n-BuMgCl 2M in diethyl ether were used. (4.07 mmol). The reagents were combined in a Schlenk tube, the tube was sealed, removed to a Schlenk line, vented to a nitrogen sparger and immersed in an oil bath maintained at 40 ° C. After two hours, the tube was returned to the drying box, where the residue was extracted with filtered and recovered pentane. The purity of the product was extremely high. The yield was 0.37 g, 74 percent. C. from (t-butylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilantitanium dihydrochloride and n-BuMgCI in DME at 20 ° C. The reaction conditions of Example 1A were substantially repeated except that 0.25 g (0.68 mmol) of (t-butylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilanetitanium dihydrochloride, 0.35 ml (13.58 mmol) of 1,3-pentadiene were used. , and 1018 ml (2.04 mmoles) of n-BuMgCI were used and the reaction mixture was stirred for three hours at room temperature (20 ° C). The purity of the product was extremely high. Example 2 Preparation of 1,2-entadiene (t-butylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilantitanium from TiCl3 »3THF and n-BuMgCI in DME heated to reflux. In a glove box under inert atmosphere, 1.0 g of CsMe4SiMe2NCMe3 [MgCl] 2 nDME having an effective molecular weight per titre of 514 g / mol (1.95 mmol) was placed in a 100 ml flask with 20 ml of DME. TiCl 3 »3THF (0.72 g, 1.95 mmol) was added and the mixture was stirred for 15 minutes. CH2Cl2 (75 μl (1.17 mmol)) was added causing the color to turn reddish brown. After 30 minutes, 3.9 ml of 1,3-pentadiene (38.91 mmol) was added followed by 2.9 ml of 2M n-BuMgCI (5.84 mmol) in diethyl ether. The color of the mixture changed to a deep purple color. The reaction mixture was refluxed for one hour, then cooled to room temperature (20 ° C) and the volatiles were removed under reduced pressure. The solid residue was extracted with pentane and the extract was filtered. The pentane was removed under reduced pressure leaving purple / black microcrystals of the desired product, which was identified by 1 H NMR analysis to be highly pure. EXAMPLE 3 Large Scale Preparation of 1,3-pentadiene of (t-butylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilantitanium from TiCl3"5DMe and n-BuMgCI A) Preparation of TiCl3» 1 5 (DME) A vessel 10 I glass (R-1) with bottom-mounted water flow valve, 5-neck head, Teflon basket, clamp and stirring components (which have arrow and vane) were fixed on the lid and purged with nitrogen. The collars were equipped as follows: the agitation components were located in the central neck and the outer collars had a reflux condenser covered with gas inlet / outlet, an inlet for solvent, a thermocouple and a retainer, respectively. Dry deoxygenated dimethyloxyethane (DME) was added to the flask (ca 4.3 I). In the drying box, 322 g of TiCl 3 were weighed into an equalizing powder addition funnel; The funnel was capped, removed from the drying box and placed in the reaction pot instead of the stopper. TiCl3 was added for about 10 minutes with stirring. After the addition was completed, additional DME was used to wash the remaining TiCl3 in the flask. The addition funnel was replaced with a stop and the mixture was heated to reflux. The color changed from purple to pale blue. The mixture was heated for about 4.5 hours. After cooling to room temperature, the solid was allowed to settle and the supernatant was decanted from the solid. The product, TiCl3 »1.5 (DME) remained in the reactor as a pale blue solid. B) Preparation of [(Me4C5) SiMe2NtBu] [MCI] 2 A 30 I glass vessel (R-2) with water flow valve mounted on the bottom, 7-necked head, Teflon basket, clamp and stirring components (which have arrow and paddle) were fixed on the lid and purged with nitrogen. The head was equipped with an agitator in the central neck and the eternal necks containing a condenator, nitrogen inlet / outlet, vacuum adapter, reagent addition tube, thermocouple and seals, respectively. The reactor was charged with 525 g of (Me4C5H) SiMe2NHtBu, followed by 5 I of toluene and then 1.57 kg of -PrMgCI 2.2M in diethyl ether. The mixture was then heated and the ether allowed to boil in a trap cooled to -78 ° C. The inert thermocouple temperature reached a maximum of 85 ° C after 2 hours of heating. At the end of this time, the heater was turned off and DME was added to the hot stirring solution, resulting in the precipitation of a white solid. The mixture was then heated again to an ambient temperature of 85 ° C and kept there for an additional hour. The solution was allowed to cool to room temperature, the material was allowed to settle and the supernatant was decanted from the solid. An additional wash was carried out by adding toluene, stirring for several minutes, allowing the solids to settle, and decanting the toluene solution. The product [(Me4C5) S1Me2NtBu] [MCI] 2 was left in R-2 as a white solvated solid. C) Preparation of [(Me4C5) SiMe2N Bu] Ti (1,3-pentadiene) The materials in R-1 and R-2 were labeled in DME (the total volumes of the mixtures were approximately 3.7 I in R-1 and 12 I in R-2). The content of R-1 was transferred into R-2 using a transfer tube connected to the bottom valve of the 10 I flask and one of the head openings in the 30 I flask. The remaining material in R-1 was washed using additional DME. The mixture darkened rapidly to a deep red / brown color. After 30 minutes, 73 ml of CH2Cl2 was added through a dropping funnel, resulting in a green / brown color change. After about 2 hours, 640 g of 1,3-pentadiene was added, followed by 2.26 kg of 2M nBuMgCI in THF. The mixture was heated to 40 ° C and stirred at this temperature for 2 hours. Then, about 7.5 I of the solvent was removed under vacuum. Then it was added to the Isopar E ™ flask (ca 5.3 I) (available from Exxon Chemical Co.). This vacuum / solvent addition cycle was repeated with approximately 5.7 I of solvent removed and 4.3 I of Isopar E ™. The material was allowed to settle, then the liquid layer was decanted into another 30 I glass container (R-3). The solids in R-2 were washed with additional Isopar E; this solution was changed with the first decanting in R-3. The solvent in R-3 was removed under vacuum to leave a red / black solid which was re-extracted with Isopar ™. This material was transferred to a storage cylinder. The analysis indicated that the solution (9.39I) was 0.1360 M in titanium. Therefore, the yield was equal to 467 g (1,277 moles) of [(Me4Cs) SiMe2NtBu] Ti (1,3-pentadiene), 61 percent based on TiCl3. Example 4 Synthesis of TiCl3 «3THF without oxidation using CH2Cl2. In the drying box, 1.0 g of [(Me4Cs) S¡Me2N, Bu] [MgCl] 2 [DME] n (effective molecular weight per titration: 514 g / mol) was placed in a 100 ml flask with 20 ml of DME. TiCl33THF (0.72 g) was added using 10 ml of additional DME. The mixture was stirred for 15 minutes, then 0.97 ml of 1,3-pentadiene was added followed by 1.46 ml of 2M nBuMgCI in THF. The color changed to a deep red / purple. The mixture was stirred for one hour. At the end of this time, volatile materials were removed under reduced pressure. The residue was extracted with pentane, the solution was filtered and the pentane was removed under reduced pressure to give a dark purple / black solid. The 1H NMR spectrum of this material indicated that it is pure [(Me4Cs) SiMe2N'Bu] Ti (1,3-pentadiene). The yield was 0.52 g, 73 percent.

Claims (3)

CLAIMS 1. A process for preparing a metal complex containing one and only one delocalized, cyclic p-linked group, said complex corresponding to the formula: X'n \ L M- wherein M is titanium or zirconium in the formal oxidation state +2: L is a group containing an anionic p-system. delocalized, cyclical, through which the group joins M and whose group is also linked to Z; Z is a portion linked to M via a s-ligation, comprising boron, or a member of Group 14 of the Periodic Table of the elements and also comprising nitrogen, phosphorus, sulfur or oxygen, said portion having up to 60 atoms that are not hydrogen; X is a neutral conjugated diene, optionally substituted with one or more hydrocarbyl groups, said Z having up to 40 carbon atoms and forming a p-complex with M; X 'is a neutral Lewis base ligand selected from amines, phosphines and ethers, said X' having from 3 to 20 atoms without hydrogen; and n is a number from 0 to 3; said process comprising contacting a metal halide compound according to the formula X'n Z X'n X * 2 M * * wherein, M * is titanium or zirconium in the formal +3 oxidation state; M ** is titanium or zirconium in the formal oxidation state +4; X * is halide; and L, Z, Z 'and n are as previously defined; with a free diene corresponding to X, and subsequently or simultaneously contacting the resulting reaction mixture with a Grignard derivative of a C-n-20 alkane to form the desired metal complex. 2. A process for preparing a metal complex containing one and only one delocalized p-linked cyclic group, said complex corresponding to the formula: X ', \ L M - X wherein, M is titanium or zirconium in the formal oxidation state +2; L is a group that contains an anionic, delocalized cyclic p-system, through which the group is bound to M and whose group also binds to Z; Z is a portion linked to M via a s-ligature, comprising boron, or a member of Group 14 of the Periodic Table of the elements, and also comprising nitrogen, phosphorus, sulfur or oxygen, said portion having up to 60 atoms that are not hydrogen; x is a conjugated neutral diene, optionally substituted with one or more hydrocarbyl groups, said x having up to 40 carbon atoms and forming a p-complex with M; X 'is a neutral Lewis base ligand of amines, phosphines and ethers, said X' having from 3 to 20 atoms that are not hydrogen; and n is a number from 0 to 3; said process comprising;

1) contacting a halide metal compound according to the formula M * (X *) 3X'no M ** (X *) 4X'no M ** (X *) 4X'n, where M * is titanium or zirconium in the formal oxidation state +3; M ** is titanium or zirconium in the formal oxidation state +4; Y X * is halide; with a dianionic salt corresponding to the formula: M * 2LZ, where: M 'is a Group 1 metal, MgCl or MgBr or two M' groups together are a Group 2 metal; to form a complex of intermediate metals according to the formula X? ' n Z X'n X * 2 M * - X * where L, Z, M **, X *, X ', M * and n are as previously defined;

2) when the metal in said intermediate metal complex is in the formal +3 oxidation state, it is optionally contacted with an intermediate metal complex with an oxidant to form an intermediate metal complex according to the formula: where L, Z, M **, X *, X 'and n are as previously defined; Y

3) contacting the intermediate metal complex with a free diene corresponding to X and subsequently or simultaneously contacting the resulting reaction mixture with a Grignard derivative of a n-alkane of C? .20 to form the complex of desired metals. 3. A process according to any claim 1 or 2, wherein the free diene corresponding to X is 1, 4-d if enyl-1, 3-butadiene; 1, 3-pentadiene; 1,4-dibenzyl-1,3-butadiene; 2,4-hexadiene; 3-methylene-1,3-pentadiene; 1,4-ditolyl-1,3-butadiene; or 1,4-bis (trimethylsilyl) -1,3-buta-diene. 4. A process according to any claim 1 or 2, wherein X is 1,3-pentadiene. 5. A process according to any claim 1 or 2, wherein the resulting metal complex corresponds to the formula: wherein: R 'each time it is presented, is independently selected from hydrogen, hydrocarbyl, silyl, germyl, halo, cyano and combinations thereof, said R' having up to 20 non-hydrogen atoms, and optionally, one or two pairs of said substituents each form a hydrocarbylene group of C2.o, thereby causing Cp to have a fused ring structure; X is a neutral 4-attached diene group, which has up to 30 non-hydrogen atoms, which forms a p-complexes with M; And it is -0 -, - S-, -NR * -. -PR * -; M is titanium or zirconium in the formal oxidation state +2; Z * is S * R * 2, CR * 2, SiR * 2 SiR * 2, CR * 2 CR * 2, CR * = CR *, CR * 2 SiR * 2, or GeR * 2; wherein: R * each time it occurs is independently hydrogen or a selected member of hydrocarbyl, silyl, halogenated alkyl, halogenated alrichl and combinations thereof, said R * having up to 10 non-hydrogen atoms. 6. A process according to claim 5, wherein R 'independently each time it is hydrogen, hydrocarbyl, silyl, halo or a combination thereof, said R' having up to 10 non-hydrogen atoms, or one or two pairs of adjacent R 'substituents together form a hydrocarbylene group of C2.o, thereby causing Cp to have a fused ring structure. 7. A process according to claim 6, wherein R 'is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl. (including where all isomers are suitable), cyclopentyl, cyclohexyl, norbornyl, benzyl or phenyl or one or two pairs of adjacent R 'substituents together cause the entire C5R' group to be an indenyl, tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl or octahydrofluorenyl. 8. A process according to claim 5, wherein Y is nitrogen or phosphorus corresponding to the formula -N (R ") - or -P (R") -, wherein R "is C1-10 hydrocarbyl. A process according to claim 5, wherein the metal complex corresponds to the formula: where M is titanium, X is? 4-1, 3-pentanediene,? 4-2,4-hexadiene,? 4-1, 4-d? f enyl-1,3-butadiene,? -3-met? L-1, 3-pentand? Ene,? 4-1, 4-d? Benc? L-1, 3-butandiene,? 4-1, 4-d? Tol? L-1, 3 -butand? ene,? 4-1 4-b? s (tr? met? l? l) -1, 3-butad? ene, R 'is hydrogen or methyl or one or two pairs of R groups together cause the ring structure to be an indenyl tetrahydroindenyl, fluorenyl or octahydrofluorenyl group, R "is d-io hydrocarbyl, R" 'is independently at each presentation hydrogen or C1-10 hydrocarbyl, E is independently whenever silicone is present or carbon, and m is 1 or 2 A process according to claim 1 or 2, wherein the reaction is carried out in a polar aprotic solvent 11. A process according to claim 10, wherein the solvent is 1,2-dimethoxyethane, tetrahydrofuran or diethyl ether. 12. A process according to claim 10, wherein the reaction is carried out in sequence in a single reactor vessel without isolation of intermediate products. 13. A process according to claim 2, wherein the oxidation is carried out by the use of a halogenated organic compound.