SYNTHESIS OF CYCLOPENTADIENYL METAL COORDINATION COMPLEXES FROM METAL HYDROCARBYLOXIDES

Abstract: A process for preparing bridged mono- and bis(cyclopendadienyl) metal dihydrocarbyloxy coordination complexes (I) by contacting in the presence of an aprotic organic diluent a metal compound of the formula M(OR)4 with a dianionic salt compound. A process for preparing bridged mono- and bis(cyclo-pentadienyl)dihydrocarbyl metal coordination complexes (II) by contacting a complex (I) with a hydrocarbylation agent. A process for preparing bridged mono- and bis(cyclopentadienyl) metal dihalide coordination complexes (III) by contacting a complex (I) with a halogenation agent.

Description: SYNTHESIS OF CYCLOPENTADIENYL METAL COORDINATION COMPLEXES FROM METAL HYDROCARBYLOXIDES The present invention relates to a process for preparing certain bridged mono- and bis-cyclopentadienyl metal dihydrocarbyloxy coordination complexes starting from metal hydrocarbyloxide compounds. The present invention also relates to a process for preparing bridged mono- and bis-cyclopentadienyl dihydrocarbyl metal coordination complexes and to a process for preparing bridged mono- and bis-cyclopentadienyl metal dihalide coordination complexes both starting from the corresponding bridged mono- or bis-cyclopentadienyl metal dihydrocarbyloxy coordination complexes. Bridged mono- and bis-cyclopentadienyl metal dihalide coordination complexes and bridged mono- and bis-cyclopentadienyl dihydrocarbyl metal coordination complexes are known and useful as addition polymerization catalysts or as components or precursors thereof . In "Metallkomplexe mit verbrueckten permethylierten Cyclopentadienylliganden" of P. Jutzi and R. Dickbreder. Chem. Ber. 119. 1750-1754 (1986) the synthesis is described of dimethylsilanediyi-bridged bis(permethylated cyciopentadienyl) titanium dichlorides from the tetrahydrof uran (THF) adducts of titanium tetrachloride and the dimethyisiianediyl-bridged bis(permethylated cyciopentadienyl) dianion derivatives. In "ansa-Metallocene derivatives: XVII. Racemic and meso diastereoisomers of group IV metallocene derivatives with symmetrically substituted, dimethylsilanediyi-bridged ligand frameworks. Crystal structure of R,S-Me 2 Si(3-t-Bu-MeC5H 2 ) 2 ZrCI 2 " of H. Wiesenfeldt et al., Journal of Or anometallic Chemistry, 369 (1989) 359-370 the synthesis is described of dimethylsilanediyi-bridged bis(substituted cyciopentadienyl) titanium dichloride complexes from the THF-adducts of titanium trichloride and the dimethylsilanediyi-bridged bis(substituted cyciopentadienyl) dianion derivatives. In "Synthesis and Complexation of Linked Cyclopentadienyl-Amido Ligands" of J. Okuda, Chem. Ber. 123 (1990) 1649-1651 the preparation is described of a bridged mono(substituted cyciopentadienyl) titanium dichloride complex from the THF-adduct of titanium tetrachloride and the dilithium salt of [(tert-butylamino)dimethylsilyl](tert- butyl)cyclopentadienide. Bridged mono-cyclopentadienyl metal dihalide coordination complexes are also prepared in USP 5,026,798 from titanium tetrachloride compounds or ether adducts thereof and the dilithium salts of bridged mono-cyclopentadienyl ligand compounds. Further, EP-A-0,416,815 teaches a process to prepare bridged mono- cyciopentadienyl metal dihalide coordination complexes starting from the transition metal tetrahalide and a Group 1 or Grignard derivative of the bridged mono-cyclopentadienyl ligand compounds. The above-mentioned synthesis methods to prepare the bridged mono- and bis- cyclopentadienyl metal dihalide coordination complexes use metal tetrahalide compounds as starting materials, which are corrosive, toxic, and air and moisture sensitive. In order to facilitate handling thereof, prior to the reaction step the transition metal tetrahalide compound istypically converted to its ether-add uct in a separate step with for example THF or diethyl ether. This adduct formation step in itself proceeds with difficulty, requiring low to very low temperatures, and an inert atmosphere. The adduct is usually recovered before it is reacted with the dianionic derivative of the ligand compound. The yield of the adduct formation step or steps is less than quantitative. Furthermore, the reaction mixture of the transition metal tetrahalide compound and the dianionic derivative of the bridged cyciopentadienyl ligand compound requires a multi-step, laborious recovery and purification procedure. Typically, after the reaction step, the solvent is removed, the product redissolved by adding dichloromethane or toluene or a mixture thereof, the metal halide byproduct, typically lithium chloride, removed by filtration of the mixture, the solvent removed at least partially, followed by redissolving the solid product and crystallizing the product, optionally followed by one or more further recrystallization procedures. Further, it is known to from EP-A-0,416,815 and EP-A-0,514,828 to prepare bridged mono-cyclopentadienyl metal dihalide coordination complexes, by reacting the THF- adduct of a transition metal trihalide compound, especially TiCI 3 , with the dianionic derivative of the cyciopentadienyl ligand. The resulting complex is contacted with a non-interfering oxidizing agent, such as for example AgCI (EP-A-0,416,815), or with an organic halide to raise the oxidation state of the metal to form the desired dihalide complex. Apart from requiring an extra reaction step, that is the oxidation step, this process also starts from the transition metal trihalide or an ether-adduct thereof which has the disadvantages listed above, and requires long reaction times to be prepared. Furthermore, the complex resulting from the reaction between the ether adduct of the transition metal trihalide compound with the dianionic derivative of the cyciopentadienyl ligand, i.e. the cyciopentadienyl metal(lll) monohalide coordination complex, is thermally unstable. The bridged mono-cyclopentadienyl dihydrocarbyl metal coordination complexes can be prepared by hydrocarbylating the corresponding bridged mono-cyclopentadienyl metal dihalide coordination complexes with a Grignard, lithium, sodium or potassium salt of the hydrocarbyl ligand. This is described, for example, in EP-A-0,418,044, example 3 and WO 92/00333. These preparation processes inherently have the disadvantages associated with the preparations of the bridged mono-cyclopentadienyl metal dihalide coordination complexes. In one aspect, the present invention relates to a process for preparing a metal dihydrocarbyloxy coordination complex corresponding to the formula: Cp* M / (I ) (OR ) . wherein: M is titanium, zirconium, or hafnium; Cp* is a cyciopentadienyl group bound in an η 5 bonding mode to M or such a cyciopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Cp* to have a fused ring structure; Z is a divalent moiety comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally sulfur or oxygen, said moiety having up to 50 non¬ hydrogen atoms, and optionally Cp* and Z together form a fused ring system; Y is a) a divalent anionic ligand group comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, said Y being bonded to Z and M through said nitrogen, phosphorus, oxygen or sulfur, and optionally Y and Z together form a fused ring system, or b) a cyciopentadienyl group bound in a sigma bonding mode to Z and in an η5 bonding mode to M or such a cyciopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Y to have a fused ring structure; and R independently each occurrence is a hydrocarbyl group having from 1 to 20 carbon atoms; the steps of the process comprising: contacting in the presence of an aprotic organic diluent a metal compound of the formula: M(OR) 4 wherein M and R are as previously defined with a dianionic salt compound corresponding to the formula: (L + *) y (Cp*-Z-Y)- 2 or ((LX) +x ) y (Cp*-Z-Y) 2 wherein: L is a metal of Group 1 or 2 of the Periodic Table of the Elements, X independently is chloro, bromo, or iodo, x and y are either 1 or 2 and the product of x and y equals 2, and Cp*, Z, and Y are as previously defined; to form the complex of formula (I). In another aspect, the present invention relates to a process for preparing a metal dihydrocarbyl coordination complex corresponding to the formula: Cp* _ M^ (I D (R , ) : wherein: M is titanium, zirconium, or hafnium; Cp* is a cyciopentadienyl group bound in an η 5 bonding mode to M or such a cyciopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Cp* to have a fused ring structure; Z is a divalent moiety comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally sulfur or oxygen, said moiety having up to 50 non¬ hydrogen atoms, and optionally Cp* and Z together form a fused ring system; Y is a) a divalent anionic ligand group comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, said Y being bonded to Z and M through said nitrogen, phosphorus, oxygen or sulfur, and optionally Y and Z together form a fused ring system, or b) a cyciopentadienyl group bound in a sigma bonding mode to Z and in an η 5 bonding mode to M or such a cyciopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Y to have a fused ring structure; and R"' independently each occurrence is a hydrocarbyl group containing from 1 to 20 carbon atoms; the process comprising contacting in the presence of an aprotic organic diluent a metal coordination complex of formula: Cp* M / (I ) (OR ) ; wherein R independently each occurrence is a hydrocarbyl group having from 1 to 20 carbon atoms and Cp*, Z, Y, M, are as previously defined; with a hydrocarbylation agent comprising a group 1, 2, 12 or 13 metal or metal derivative and at least one hydrocarbyl group R"', to form the metal dihydrocarbyl coordination complex of formula (II). In yet another aspect the present invention relates to a process for preparing a metal dihalide coordination complex corresponding to the formula: Cp* M / (III ) (X ' ) : wherein: ■ M is titanium, zirconium, or hafnium; Cp* is a cyciopentadienyl group bound in an η5 bonding mode to M or such a cyciopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Cp* to have a fused ring structure; Z is a divalent moiety comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally sulfur or oxygen, said moiety having up to 50 non¬ hydrogen atoms, and optionally Cp* and Z together form a fused ring system; Y is a) a divalent anionic ligand group comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, said Y being bonded to Z and M through said nitrogen, phosphorus, oxygen or sulfur, and optionally Y and Z together form a fused ring system, or b) a cyciopentadienyl group bound in a sigma bonding mode to Z and in an n 5 bonding mode to M or such a cyciopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Y to have a fused ring structure; and X' independently each occurrence is a halo group; the process comprising contacting in the presence of an aprotic organic diluent a metal coordination complex of formula: Cp* M / (I ) (OR ) . wherein R independently each occurrence is a hydrocarbyl group having from 1 to 20 carbon atoms and Cp*, Z, Y, M, are as previously defined; with a halogenation agent comprising at least a member of Group 13 or 14 of the Periodic Table of the Elements and at least one halo group X', to form the metal dihalide coordination complex of formula (III). All reference to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 1989. Also, any reference to a Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering Groups. Surprisingly, it has been found that two hydrocarbyloxy groups on the titanium, zirconium, or hafnium (hereinafter referred to as Group 4 metal) center can be removed readily by contacting the compound M(OR) where M and R are as previously defined with the dianionic salt compound to give the complexes of formulas (I), (la), or (lb) in high yield and high purity. This discovery was indeed surprising as hydrocarbyloxy-transition metal bonds are considered to be stronger bonds than halogen-transition metal bonds and therefore the hydrocarbyloxy groups are considered less suitable leaving groups than halogen groups. The starting Group 4 metal hydrocarbyloxy compounds, typically the titanium tetraisopropoxide, tetra-n-butoxide and tetra-t-butoxide, are non-viscous liquids, only mildly air-sensitive, commercially available, and readily soluble in hydrocarbons, as compared to the corrosive, air- sensitive and difficult to handle Group 4 metal tetrachlorides. This new process typically provides the complexes of formulas (I), (la), and (lb) in yields of 90 percent and higher. The product complexes can be readily isolated in high purity by filtration. In the present process bridged mono- or bis(cyclopentadienyl) metal dihydrocarbyloxy coordination complexes of formulas (I), (la), or (lb) are prepared by contacting a Group 4 metal tetrahydrocarbyloxy compound of the formula: M(OR) 4 , wherein M and R are as previously defined, with a dianionic salt compound. The dianionic salt is preferably a double Group 1 metal derivative or double Grignard (Group 2 metal monohalide) derivative of the -Cp*-Z-Y- moiety, the anionic charges formally residing on the Cp* and Y groups. In the relevant part of the formula for the dianionic salt compound the double Group 1 metal derivative corresponds to (L +X ) y wherein x is 1 and y is 2, and the double Grignard derivative corresponds to ((LX) +x ) y wherein x is 1 and y is 2. In the metal dihydrocarbyloxy coordination complexes of formula (I), M is titanium, zirconium, or hafnium and R independently each occurrence is a hydrocarbyl group having from 1 to 20 carbon atoms, more preferably R each occurrence is independently selected from the group consisting of alkyl, aryl, alkaryl, and aralkyl groups, even more preferably from alkyl groups having from 1 to 6 carbon atoms, and aryl, aralkyl and alkaryl groups having from 6-10 carbon atoms, and most preferably R each occurrence is independently selected from the group consisting of ethyl, isopropyl, n-butyl, and t-butyl. A neutral Lewis base, such as an ether or amine compound, may also be associated with the complex, if desired, however, such is generally not preferred. The term "substituted cyciopentadienyl" includes, but is not limited to, indenyl, tetrahydroindenyl, f luorenyl, tetrahydrof luorenyl, and octahydrof luorenyl groups. Generic formula (I) embraces bridged monocyclopentadienyl metal dihydrocarbyloxy coordination complexes and bridged bis(cyclopentadienyl) metal dihydrocarbyloxy coordination complexes. Preferred bridged monocyclopentadienyl metal dihydrocarbyloxy coordination complexes of formula (I) prepared in the present process include those having constrained geometry. By the term "constrained geometry" as used herein is meant that the metal atom in the metal coordination complex and also in the catalyst resulting therefrom is forced to greater exposure of the active catalyst site because of a specific ring structure of a ligand group including the metal atom, wherein the metal is both bonded to an adjacent covalent moiety and held in association with the delocalized π-bonded cyciopentadienyl group through an η 5 or other π-bonding interaction. It is understood that each respective bond between the metal atom and the constituent atoms of the π-bonded moiety need not be equivalent. That is, the metal may be symmetrically or unsymmetrically π-bound thereto. The concept of constrained geometry and specific constrain inducing ligand groups are described in more detail in U.S. Patent Application Serial Number 545,403, filed July 3, 1990 (corresponding to EP-A-0,416,815) which is incorporated herein by reference. Suitable examples of moiety Z in formula (I) include SiR * 2 , CR * 2 , SiR* 2 SiR* 2 , CR * 2 CR * 2 , CR* = CR* ( CR * 2 SiR* 2 , GeR * 2 , or BR* wherein R* each occurrence is independently selected from the group consisting of hydrogen, alkyl, aryl, silyl, halogenated alkyl, halogenated aryl groups having up to 20 non-hydrogen atoms, and mixtures thereof, or two or more R* groups from Z, or an R* group from Z together with Y form a fused ring system. Further more preferably, Y in formula (I) is -0-, -S-, -NR * -, -PR * -. Highly preferably Y is a nitrogen or phosphorus containing group corresponding to the formula -N(R')- or -P(R')-, i.e. an amido or phosphido group, wherein R' is as defined hereinafter. More preferably, in the present process is prepared a metal coordination dihydrocarbyloxy complex of formula (I) corresponding to the formula: wherein R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms, or two R' groups together form a divalent derivative thereof; E is silicon or carbon; m is 1 or 2; and M and R are as previously defined; and wherein the metal compound of the formula: M(OR) 4 is contacted with a dianionic salt compound corresponding to the formula: (L +x ) y (C 5 R' -(ER' 2 ) m -NR')- 2 or ((LX) + *) y (C 5 R' 4 -(ER' 2 )m-NR')- 2 wherein L, R', E, X, x, y, and m are as previously defined. It is remarked that when a substituent, such as R', on a cyciopentadienyl group is hydrogen, halo or cyano, two of such substituents can not together form a divalent derivative thereof or cause the groups to have a fused ring structure. In the complexes of formula (la), M is preferably titanium, and preferably R independently each occurrence is alkyl, aryl, aralkyl, and alkaryl groups, more preferably selected from an alkyl group having from 1 to 6 carbon atoms, and aryl, aralkyl and alkaryl groups having from 6-10 carbon atoms, even more preferably R is a C-*. -alkyl, and especially ethyl, isopropyl, n-butyl, or t-butyl. Examples of the above most highly preferred metal dihydrocarbyloxy coordination compounds include compounds wherein the R' on the amido group is methyl, ethyl, propyl, butyl, pentyl, hexyl, and isomers of these alkyl radicals, norbornyl, benzyl, phenyl, etc.; the cyciopentadienyl group is cyciopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl, octahydrofluorenyl, etc.; R' on the foregoing cyciopentadienyl groups each occurrence is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, and isomers of these alkyl radicals, norbornyl, benzyl, phenyl, etc.; and R is ethyl, isopropyl, n-butyl or t-butyl. Specific highly preferred compounds include: (tert-butylamido)(tetramethyl-η5- cyclopentadienyl)-1 ,2-ethanediyltitanium di-ethoxide, (tert-butylamido)(tetramethyl-η 5 - cyciopentadienyl)- 1 ,2-ethanediyltitanium di-isopropoxide, (tert-butylamido)(tetramethyl-η 5 - cyclopentadienyl)-1 ,2-ethanediyltitanium di-n-butoxide, (tert-butylamido)(tetramethyl-η 5 - cyclopentadienyl)dimethylsilanetitanium di-ethoxide, (tert-butylamido)(tetramethyl-η 5 - cyclopentadienyl)dimethylsilanetitanium di-isopropoxide, (tert-butylamido)(tetramethyl-η 5 - cyclopentadienyl)dimethylsilanetitanium di-n-butoxide, (methylamido)(tetramethyl-η 5 - cyciopentadieny dimethylsilanetitanium di-ethoxide, (methylamido)(tetramethyl-η 5 - cyclopentadieny dimethylsilanetitanium di-isopropoxide, (methylamido)(tetramethyl-η 5 - cyclopentadienyl)dimethylsilanetitanium di-n-butoxide, (phenylamido)(tetramethyl-η 5 - cyclopentadienyl)dimethylsilanetitanium di-ethoxide, (phenylamido)(tetramethyl-η5- cyclopentadienyl)dimethylsilanetitanium di-isopropoxide, (phenylamido)(tetramethyl-η 5 - cyclopentadienyl)dimethylsilanetitanium di-n-butoxide, (be nzylamido)(tetramethyl-η 5 - cyclopentadienyl)dimethylsilanetitanium di-ethoxide, (benzylamido)(tetramethyl-η 5 - cyclopentadienyl)dimethylsilanetitanium di-isopropoxide, (benzylamido)(tetramethyl-η 5 - cyclopentadienyl)dimethylsilanetitanium di-n-butoxide, (tert-butylamido)(η5- cyciopentadienyl)- 1 ,2-ethanediyltitanium di-ethoxide, (tert-butylamido)(η5-cyclopentadienyl)- 1 ,2-ethanediyltitanium di-isopropoxide, (tert-butylamido)(η5-cyclopentadienyl)-1 ,2- ethanediyltitanium di-n-butoxide, (tert-butylamido)(η5-cyclopentadienyl)- dimethylsilanetitanium di-ethoxide, (tert-butylamido)(η5-cyclopentadienyl)- dimethylsiianetitanium di-isopropoxide, (tert-butylamido)(η5- cyclopentadienyl)dimethylsilanetitanium di-n-butoxide, (methylamido)(η5- cyclopentadieny dimethylsilanetitanium di-ethoxide, (methylamido)(η5- cyclopentadienyl)dimethylsilanetitanium di-isopropoxide, (t-butylamido)(η5-cyclopenta- dienyl)dimethylsilanetitanium di-n-butoxide, (t-butylamido)indenyldimethylsilanetitanium di- ethoxide, (t-butylamido)indenyldimethylsilanetitanium di-isopropoxide, (t- butylamido)indenyldimethylsilanetitanium di-n-butoxide, (benzylamido)indenyldimethyisilanetitanium di-ethoxide, and (benzylamido)indenyldimethylsilanetitanium di-isopropoxide. According to another preferred embodiment of the present process, there is prepared a metal coordination complex of formula (I) corresponding to the formula: wherein: R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non¬ hydrogen atoms, or two R' groups together form a divalent derivative thereof; E is silicon or carbon; R" independently each occurrence is hydrogen or a group selected from silyl, hydrocarbyl and combinations thereof, said R" having up to 30 carbon or silicon atoms; m is 1 to 8; and M and R are as previously defined; and wherein the metal compound of the formula: M(OR) 4 is contacted with a dianionicsalt compound corresponding to the formula: (L + *) y (C 5 RV(ER"2)m-C 5 R'4)- 2 or ((LX) + *) y (C5R'4-(ER"2)m-C 5 R'4)- 2 wherein L, R', E, R", X, m, x and y are as previously defined. Exemplary metal complexes of bridged bis-cyclopentadienyl metal dihydrocarbyloxy coordination complexes include those complexes of formula (lb) wherein E is silicon or carbon, R" independently each occurrence is hydrogen or a group selected from silyl, hydrocarbyl and combinations thereof, said R" having up to 30 carbon or silicon atoms, and m is 1 to 8. Preferably R" independently each occurrence is methyl, benzyl, tert-butyl, or phenyl. Such bridged bis(cyclopentadienyl) structures are especially suited for use as catalysts, or precursors thereof, for the preparation of polymers having stereoregular molecular structure. In such capacity it is preferred that the complex be nonsymmetrical or possess a chiral, stereorigid structure. Examples of the first type are compounds possessing different delocalized π-bonded systems, such as one cyclopenta-dienyl group and one indenyl group. Examples of chiral structures include bis-indenyl complexes. Exemplary bridged bis(cyclopentadienyl) metal dihydrocarbyloxy complexes of formula (lb) are those wherein the bridged ligand group is: dimethylsilyl-bis-cyclopentadienyl, dimethylsilyl-bis-tetramethylcyclopentadienyl, dimethylsilyl-bis-indenyl, isopropylidene- cyclopentadienyl-f luorenyl, 2,2'-biphenyldiylbis(3,4-dimethyl-1 -cyciopentadienyl), and 6,6-dimethyl-2,2'-biphenylbis(3,4-dimethyl-1-cyclopentadienyl). In a preferred embodiment, the moiety ((LX)+ χ ) y in the dianionic salt compound corresponds to ((MgCI)+) 2 . In another preferred embodiment, the moiety (L+ x ) 2 in the dianionic salt corresponds to (Li + ) 2 . Use of the former dianionic salt compound in the present process gives as a byproduct MgCI(OR) which can be easily separated from the desired product. The molar ratio of the dianionic salt compound to the metal dihydrocarbyloxy compound M(OR) 4 can vary between wide limits. Although an improved process can be obtained with dianionic salt compound to metal compound molar ratios of 0.5: 1 and higher, for example, up to 10 : 1 , or preferably up to 5 : 1 , the yield of the process and the purity of the desired products are high at ratios of 1 : 1 and slightly higher, for example, up to 1.5: 1 , preferably up to 1.2: 1. In the present process an aprotic organic diluent is used. Suitable examples of such diluents are ethers and hydrocarbons. Preferably the hydrocarbon solvent is an aliphatic or cycloaliphatic hydrocarbon solvent having from 5 to 10 carbon atoms. Suitable solvents are pentane, hexane, heptane, Isopar E (a mixture of isoparaffinic hydrocarbons available from Exxon Chemical Inc.), isooctane, cyclohexane, and methylcyclohexane. Carrying out the reaction in a hydrocarbon solvent has the advantage that the product dihydrocarbyloxy complexes of formulas (I), (la), and (lb) are soluble, whereas the byproduct L-OR or LX-OR generally is not. The desired products thus can be easily recovered, if desired, by filtration or other liquid-solid separation methods. By subjecting the liquid thus obtained to a stripping step to strip off the volatile solvent a highly pure product is obtained. The temperature at which the process is conducted is not critical, but is preferably below the boiling point of the diluent. Preferred temperatures range from 0°C to 100°C, more preferably from 10°C to 80°C, and most preferably from 20° to 60°C. Generally the reactants are contacted under an inert atmosphere for a time from several minutes to several days. The presence of oxygen and moisture are preferably avoided. The reactants can be added in any order. Agitation may be employed if desired. According to a further aspect the present invention provides a process for preparing bridged mono- or biscyclopentadienyl dihydrocarbyl metal coordination complexes of formulas (II), (lla), and (lib) by contacting a corresponding metal dihydrocarbyloxy coordination complex of formula (I), (la), or (lb) obtainable as described hereinbefore with a hydrocarbylation agent comprising a Group 1, 2, 12 or 13 metal or metal derivative and at least one hydrocarbyl group R"', to form the dihydrocarbyl metal coordination complex of formula (II), (lla) or (lib). Surprisingly, it has been found that the dihydrocarbyloxy complexes of formulas (I), (la), and (lb) are stable compounds which can readily be converted to the corresponding dihydrocarbyl compounds of formulas (II), (lla), or (Mb) in high yields and purity. The present hydrocarbylation process, especially in combination with the process for preparing the metal dihydrocarbyloxy coordination complexes of formulas (I), (la), or (lb) as described herein before, enables the valuable complexes of formulas (II), (lla), or (lib) to be prepared in high overall yields compared to a process starting from metal tetrahalide compounds. In a preferred embodiment, a metal dihydrocarbyl coordination complex corresponding to the formula: wherein R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms, or two R' groups together form a divalent derivative thereof; E is silicon or carbon; m is 1 or 2; and M and R"' are as previously defined; is prepared by contacting a metal dihydrocarbyloxy coordination complex corresponding to the formula: wherein: M, R', E, R, and m are as previously defined; with the hydrocarbylation agent. In another preferred embodiment, a metal dihydrocarbyl coordination complex corresponding to the formula: wherein: R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non¬ hydrogen atoms, or two R' groups together form a divalent derivative thereof; E is silicon or carbon; R" independently each occurrence is hydrogen or a group selected from silyl, hydrocarbyl and combinations thereof, said R" having up to 30 carbon or silicon atoms; m is 1 to 8; and M and R"' are as previously defined; is prepared by contacting a metal dihydrocarbyloxy coordination complex corresponding to the formula: wherein R', E, R", M, R, and m are as previously defined; with the hydrocarbylation agent. In a further preferred embodiment, the metal dihydrocarbyloxy coordination • complex of formula (I), (la), or (lb), used as starting compound in the preparation of complexes of formulas (II), (lla) or (lib), is prepared by contacting in the presence of an aprotic organic diluent a metal compound of the formula: M(OR) 4 wherein M and R are as previously defined with a dianionic salt compound corresponding to the formula: (L + *) y (Cp*-Z-Y)- 2 or ((LX) +x ) y (Cp*-Z-Y)- 2 wherein: L is a metal of Group 1 or 2 of the Periodic Table of the Elements, X independently is chloro, bromo, or iodo, x and y are either 1 or 2 and the product of x and y equals 2, and Cp*, Z, and Y are as previously defined; optionally followed by recovering the complex corresponding to formula (I). In the complexes of formulas (I), (la), and (lb), M is titanium, zirconium, or hafnium and R independently each occurrence is a hydrocarbyl group having from 1 to 20 carbon atoms, preferably R each occurrence is independently selected from the group consisting of alkyl, aryl, aralkyl, and alkaryl groups, more preferably alkyl groups having from 2 to 6 carbon atoms and aryl, aralkyl, and alkaryl groups having from 6-10 carbon atoms, and most preferably R each occurrence is independently selected from the group consisting of ethyl, isopropyl, n-butyl, and t-butyl. Preferred embodiments of the present process to prepare the complexes of formulas (I), (la), and (lb) are illustrated hereinbefore and hereby incorporated by reference. The complexes of formulas (I), (la), and (lb) as obtained can be recovered or purified, if desired, prior to proceeding with the hydrocarbylation step. The hydrocarbyl group R"' in formulas (II), (lla), and (lib) and present in the hydrocarbylation agent generally has from 1 to 20 carbon atoms and can be an aliphatic, cycloaliphatic, or aromatic hydrocarbon or a mixture thereof. Preferably, R"' is selected from the group consisting of alkyl, aryl and aralkyl groups, more preferably from alkyl groups having from 1 to 6 carbon atoms, or aralkyl groups having from 7 to 10 carbon atoms. Most preferably R"' is methyl, neopentyl, or benzyl. The hydrocarbylation agent comprises a Group 1 , 2, 12 or 13 metal or metal derivative and at least one hydrocarbyl group R"'. Suitable examples of the hydrocarbylation agent include LiR"', MgR'" 2 , MgR"'X" (wherein X" is halogen, preferably chloro), AIR'" 3 , and R"'-substituted aluminoxane. Suitable R"'-substituted aluminoxanes preferably include Cι.6- alkylaluminoxanes, especially methylaluminoxane. Alkylaluminoxanes are well known in the art and methods for their preparation are illustrated by U.S. Patent Nos. 4,592,199; 4,544,762; 5,015,749 and 5,041,585. Preferably, the hydrocarbylation agent comprises LiR'" or AIR'" 3 . More preferably the hydrocarbylation agent is trialkyl aluminum, most preferably trimethyl aluminum. Specific highly preferred complexes of formula (lla) include: (tert- butylamido)(tetramethyl-η 5 -cyclopentadienyl)-1,2-ethanediyltitanium dimethyl, (tert- butylamido)(tetramethyl-η 5 -cyclopentadienyl)-1,2-ethanediyltitanium dibenzyl, (tert- butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium dimethyl, (tert- butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium dibenzyl, (methylamido)(tetramethyl-η5-cyclopentadienyl)dimethylsilanetitanium dimethyl, (methylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium dibenzyl, (phenylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium dimethyl, (phenylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium dibenzyl, (benzylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium dimethyl, (benzylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium dibenzyl, (tert- butylamido)(η5-cyclopentadienyl)-1 ,2-ethanediyltitanium dimethyl, (tert-butylamido)(η5- cyclopentadienyl)-1,2-ethanediyltitanium dibenzyl, (tert-butylamido)(η5-cyclopentadienyl)- dimethylsilanetitanium dimethyl, (tert-butylamido)(η5- cyclopentadienyl)dimethylsilanetitanium dibenzyl, (methylamido)(η5- cyclopentadienyl)dimethylsilanetitanium dimethyl, (t-butylamido)(η5-cyciopenta- dienyl)dimethylsilanetitanium dibenzyl, (t-butylamido)indenyldimethylsilanetitanium dimethyl, (t-butylamido)indenyldimethylsilanetitanium dibenzyl, and (benzylamido)indenyldimethylsilanetitanium dibenzyl. The molar ratio of the hydrocarbylation agent to the complex of formulas (I), (la), and (lb) can vary between wide limits, but is preferably between 0.1 : 1 and 20: 1 , more preferably between 0.5: 1 to 10: 1. Advantageously, an equivalent amount or a slight excess of R"'-groups in the hydrocarbylation agent is used with respect to the metal hydrocarbyloxy compound of formulas (I), (la), or (lb), i.e., a ratio of from 2.0: 1 to 4.0: 1 , more preferably of from 2.1 :1 to 3: 1. The temperature at which the hydrocarbylation step is conducted is not critical, but is preferably below the boiling point of the aprotic organic diluent Preferred temperatures range from 0°C to 100°C, more preferably from 10°C to 80°C. Generally the reactants are contacted under an inert atmosphere for a time from several minutes to several days. The reactants can be added in any order. Agitation may be employed if desired. In the present hydrocarbylation step an aprotic organic diluent is used. Preferably, diluents are used in which the complexes of formulas (I), (la), and (lb) are readily soluble, optionally upon heating. Suitable examples of such solvents are ethers and hydrocarbons. Preferably the solvent is a hydrocarbon, advantageously an aliphatic or cycloaliphatic hydrocarbon solvent having from 5 to 10 carbon atoms. Suitable solvents are pentane, hexane, heptane, Isopar E, isooctane, cyclohexane, and methylcyclohexane. Carrying out the reaction in a hydrocarbon solvent has the advantage that the product hydrocarbyl complexes of formulas (II), (lla), and (lib) are soluble and non-volatile, while the byproduct Group 1, 2, 12 or 13 metal or metal derivative hydrocarbyloxides are often either insoluble or volatil, especially when R is a lower alkyl, such as a C-*_ alkyl. Thus, the byproducts LiOR and Mg(OR)R"' generally are not soluble in hydrocarbons when R is a lower alkyl, and may be easily removed from the desired hydrocarbyl product by filtration, decantation, or other liquid-solid separation method. By subjecting the liquid thus obtained to a stripping step to remove the volatile solvent a highly pure product may be obtained. However, the byproduct formed when using the highly preferred trimethylaluminum as the hydrocarbylation agent comprises a dimethylaluminum hydrocarbyloxide which is volatile. This byproduct can be removed from the desired product by applying a vacuum so as to remove both the byproduct and the solvent/diluent in one step. According to another aspect the present invention provides a process for preparing bridged mono- or bis(cyclopentadienyl) metal dihalide coordination complexes of formulas (III), (Ilia) or (1Mb) by contacting a corresponding metal dihydrocarbyloxy coordination complex of formula (1), (la), or (lb) obtainable as described hereinbefore, with a halogenation agent comprising a Group 13 or 14 element or derivative thereof and at least one halo group X'. to form the metal dihalide coordination complex of formulas (III), (Ilia) or (lllb). Surprisingly, it has been found that the dihydrocarbyloxy complexes of formulas (I), (la) or (b) are stable compounds which can easily be converted to the corresponding dihalide compounds of formulas (III), (Ilia) or (lllb) in high yields and purity. The present halogenation process, especially in combination with the process for preparing the metal dihydrocarbyloxy coordination complexes of formulas (I), (la) or (lb) as described herein before, enables the complexes of formulas (III), (Ilia) or (lllb) to be prepared in high yields compared to a process starting from metal tetrahalide compounds. In a preferred embodiment, a metal dihalide coordination complex corresponding to the formula (Ilia): wherein R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms, or two R' groups together form a divalent derivative thereof; E is silicon or carbon; m is 1 or 2; and M and X' are as previously defined; is prepared by contacting a metal dihydrocarbyloxy coordination complex corresponding to the formula: wherein: M, R', E, R, and m are as previously defined; with the halogenation agent. In another preferred embodiment, a metal dihalide coordination complex correspond wherein: R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non¬ hydrogen atoms, or two R' groups together form a divalent derivative thereof; E is silicon or carbon; R" independently each occurrence is hydrogen or a group selected from silyl, hydrocarbyl and combinations thereof, said R" having up to 30 carbon or silicon atoms; m is 1 to 8; and M and X' are as previously defined; is prepared by contacting a metal dihydrocarbyloxy coordination complex corresponding to the formula: wherein R', E, R", M, R, and m are as previously defined; with the halogenation agent. In a further preferred embodiment, the metal dihydrocarbyloxy coordination complex of formulas (I), (la) or (lb), used as starting compound in the preparation of complexes of formulas (III), (Ilia) or (lllb), is prepared by contacting in the presence of an aprotic organic diluent a metal compound of the formula: M(OR) 4 wherein M and R are as previously defined with a dianionic salt compound corresponding to the formula: (L + *) (Cp*-Z-Y)- 2 or ((LX) +» ) (Cp*-Z-Y)- 2 wherein: L is a metal of Group 1 or 2 of the Periodic Table of the Elements, X independently is chloro, bromo, or iodo, x and y are either 1 or 2 and the product of x and y equals 2, and Cp*, Z, and Y are as previously defined; optionally followed by recovering the complex corresponding to formula (I). in the complexes of formulas (I), (la), and (lb), M is titanium, zirconium or hafnium and R independently each occurrence is a hydrocarbyl group having from 1 to 20 carbon atoms, preferably R each occurrence is independently selected from the group consisting of alkyl, aryl, aralkyl, and alkaryl groups, more preferably alkyl groups having from 2 to 6 carbon atoms and aryl, aralkyl, and alkaryl groups having from 6-10 carbon atoms, and most preferably R each occurrence is independently selected from a C-|. -alkyl, especially from the group consisting of ethyl, isopropyl, n-butyl, and t-butyl. Preferred embodiments of the present process to prepare the complexes of formulas (I), (la), and (lb) are illustrated hereinbefore and hereby incorporated by reference. The complexes of formulas (I), (la), and (lb) as obtained can be recovered or purified, if desired, before proceeding with the halogenation process. The halo group X' in formulas (III), (Ilia), and (lllb) and in the halogenation agent can be chloro, bromo, or iodo, but is preferably chloro. The halogenation agent comprises a Group 13 or 14 element or derivative thereof and at least one halo group X. Suitable examples of the halogenation agent include the halides, preferably chlorides, of boron, aluminum and silicon and acetyl halides such as acetyl bromide and acetyl chloride. Preferably, the halogenation agent is selected from the group consisting of silicon tetrachloride, boron trichloride, and alkylaluminum chlorides, more preferably dialkylaluminum chlorides such as diethylaluminum chloride. Most preferred halogenation agents are silicon tetrachloride and boron trichloride. Specific highly preferred complexes of formula lllb include: (tert- butylamido)(tetramethyl-η 5 -cyclopentadienyl)-1,2-ethanediyltitanium dichloride, (tert- butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium dichloride, (methylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium dichloride, (phenylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium dichloride, (benzylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium dichloride, (tert- butylamido)(η5-cyclopentadienyl)-1 ,2-ethanediyltitanium dichloride, (tert-butylamido)(η5- cyclopentadienyl)dimethylsilanetitanium dichloride, (methylamido)(η5- cyclopentadienyl)dimethylsilanetitanium dichloride, and (t-butylamido)indenyldimethylsilane- titanium dichloride. The molar ratio of the halogenation agent to the complex of formulas (I), (la), and (lb) can vary between wide limits, but is preferably between 0.1 : 1 and 20: 1 , more preferably between 0.5: 1 to 10: 1. Advantageously, an equivalent amount or slight stoichiometric excess of halogenation agent is used with respect to the metal dihydrocarbyloxy compound of formula (I), (la) or (lb), i.e. a ratio of 2.0: 1 to 4.0: 1 , more preferably of from 2.1 : 1 to 3: 1. The temperature at which the halogenation step is conducted is not critical, but is preferably below the boiling point of the diluent. Preferred temperatures range from 0°C to 100°C, more preferably from 10°C to 80°C. Generally the reactants are contacted under an inert atmosphere for a time from several minutes to several days. The reactants can be added in any order. Agitation may be employed if desired. In the present halogenation step an aprotic organic diluent is used. Preferably, diluents are used in which the complexes of formulas (I), (la), and (lb) are readily soluble, optionally upon heating. Suitable examples of such solvents are ethers and hydrocarbons. Preferably the solvent is a hydrocarbon, advantageously an aliphatic or cycloaliphatic hydrocarbon solvent having from 5 to 10 carbon atoms. Suitable solvents are pentane, hexane, heptane, Isopar E, isooctane, cyclohexane, and methylcyclohexane. In general, isolation of the desired complexes can take place as required by the byproducts. Removal of volatiles, such as the solvent, is preferably carried out by vacuum distillation at elevated temperatures. When silicon tetrachloride is used as halogenation agent the byproduct formed comprises a hydrocarbyloxy silicon chloride. Byproducts containing lower alkyls in the hydrocarbyloxy portion, especially C-*. 4 alkyls, may be volatile. These volatile byproducts can be easily removed from the desired product by using vacuum distillation. Highly pure products are generally obtained, as compared to the prior art methods which require extensive filtration and recrystallization steps. The compounds prepared with the processes according to the present invention, that is the complexes of formulas (I), (la), (lb), (II), (lla), (lib), (III), (Ilia) and (lllb) can be used as components of catalyst systems, or precursors therefor, useful in addition polymerization processes. in a process for preparing a polymer of one or more addition polymerizable monomers, a catalyst comprising a metal coordination complex of any of the above-mentioned formulas and an activating cocatalyst are contacted with one or more addition polymerizable monomers under addition polymerization conditions. Suitable activating cocatalysts are, for example, described in U.S. Patent Application Nos. 545,403, filed July 3, 1990 (corresponding to EP-A-0,416,815) and 817,202, filed January 6, 1992 (corresponding to WO-A-92/ 10360), which are incorporated herein by reference. Preferred examples of activating cocatalysts include alumoxanes, advantageously methylalumoxane, tris(perfluorophenyl) borane, and tetra(perfluorophenyl) borates. "Addition polymerizable monomers" include for example ethylenically unsaturated monomers, conjugated or nonconjugated dienes, polyenes, etc. Preferred monomers include the C 2 -ιo α-olefins especially ethylene, propylene, isobutylene, 1-butene, 1- hexene, 4-methyl-1-pentene, and 1-octene. Other preferred monomers include styrene, halo- or alkyl substituted styrene, vinylbenzocyclobutane, 1,4-hexadiene, ethylidenenorbornene, cyclopentene, and norbornene. Suitable catalysts for use according to the present invention are prepared by combining the metal coordination complex of formulas (I), (II), or (III) and activating cocatalyst compound in any order and in any suitable manner. Preferably the ratio of the coordination complex and cocatalyst on a molar basis is from about 1 :0.1 to about 1 : 10,000. It will, of course, be appreciated that the catalyst system may also be formed in situ if the components thereof are added directly to the polymerization process and a suitable solvent or diluent, including condensed monomer, is used in said polymerization process. Suitable solvents include toluene, ethylbenzene, alkanes and mixtures thereof. In certain cases the catalysts may be isolated from solution and retained under inert atmosphere prior to use. The catalysts' components are sensitive to both moisture and oxygen and should be handled and transferred in an inert atmosphere such as nitrogen, argon or helium or under vacuum. The polymerization is conducted according to known techniques for Ziegler- Natta or Kaminsky-Sinn type polymerizations. That is, the monomer(s) and catalyst are contacted at a temperature from -30°C to 250°C, at reduced, elevated or atmospheric pressures. The polymerization is conducted under an inert atmosphere which may be a blanketing gas such as nitrogen, argon, hydrogen, ethylene, etc. or under vacuum. Hydrogen may additionally be utilized in the control of molecular weight through chain termination as is previously known in the art. The catalyst may be used as is or supported on a suitable support such as alumina, MgCI 2 or silica to provide a heterogeneous supported catalyst. A solvent may be employed if desired. Suitable solvents include toluene, ethylbenzene, alkanes and excess vinyl aromatic or olef in monomer. The reaction may also be conducted under solution or slurry conditions, in a suspension utilizing a perf luorinated hydrocarbon or similar liquid, in the gas phase, i.e. utilizing a fluidized bed reactor, or in a solid phase powder polymerization. A catalytically effective amount of the present catalyst and cocatalyst is any amount that successfully results in formation of polymer. Such amounts may be readily determined by the routine experimentation by the skilled artisan. Preferred amounts of catalyst and cocatalyst are sufficient to provide an equivalent ratio of addition polymerizable monomer: catalyst of from 1 X 10 10 : 1 to 100: 1 , preferably from 1 X 10 8 : 1 to 500: 1 , most preferably 1 X 10 6 : 1 to 1000: 1. The cocatalyst is generally utilized in an amount to provide an equivalent ratio of cocatalyst: catalyst from 10,000: 1 to 0.1 : 1, preferably from 1,000: 1 to 1 : 1. It is to be understood that the metal complex may undergo various transformations or form intermediate species prior to and during the course of a polymerization. The resulting polymeric product is recovered by filtering or other suitable technique. Additives and adjuvants may be incorporated in the polymers of the present invention in order to provide desirable characteristics. Suitable additives include pigments, UV stabilizers, antioxidants, blowing agents, lubricants, plasticizers, photosensitizers, and mixtures thereof. Having described the invention, the following examples are provided to further illustrate the same and are not to be construed as limiting. Example 1 : Preparation of (tert-butylamido)dimethyl(tetramethyl-n 5 -cvclopentadienyl)silane titanium diisopropoxide In a drybox, 24.95 g of titaniumtetraisopropoxide (Ti(0*Pr) 4 ) (Aldrich Chemical Company) (88 mmol) was dissolved in about 200 ml of hexane. 58 g of solid di(chloromagnesium) (tert-butylamido)-dimethyl(tetramethylcyclopentadienyl)silane 0 complexed with dimethoxyethane, [Me 4 C 5 SiMe 2 N*Bu][MgCI] 2 (DME) n (effective molecular weight by titration: about 629 g/mole; 92 mmol)(prepared according to the following procedure: In an apparatus consisting of a 3 I round bottom flask which was equipped with a stirrer, a condenser, and a nitrogen inlet was loaded 500 ml of toluene, followed by 106 g of Me 4 C 5 HSiMe 2 NHtBu, and then 380 ml of 2.2 M 'PrMgCl in Et 2 0. The mixture was then heated, 5 and the ether removed by distillation and trapped in a condenser cooled to -78°C. After five hours of heating, the heater was turned off, and 450 ml of dimethoxyethane (DME) was slowly added to the hot, stirred solution, resulting in the precipitation of a white solid. The solution was allowed to cool to room temperature, the solid was allowed to settle, and the supernatant was decanted from the solid. The solid was resuspended in Isopar E and filtered. 210 g (79 0 percent yield) [Me 4 C5SiMe 2 N t Bu][MgCI] 2 (DME) n was obtained as off-white solid.) was added to the flask, using about 50 ml of additional hexane. The mixture was stirred overnight at room temperature, then filtered through a medium porosity fritted glass filter (10-15 μm porosity). The solids remaining on the frit were washed with additional hexane until the washings are colorless. A yellow/orange solution was obtained, and the volatile materials were removed 5 from this solution under reduced pressure to leave (Me 4 C 5 SiMe 2 N t Bu)Ti(O i Pr) 2 as a yellow crystalline solid in essentially quantitative yield. 1 H NMR (C 6 D 6 ): 4.57 ppm (septet, 2H), 2.16 ppm (s, 6H), 1.91 ppm (s, 6H), 1.37 ppm (s, 9H), 1.15 ppm (d, 12H), and 0.65 ppm (6H). Example 2: Preparation of (tert-butylamido)dimethyl(tetramethyl-n 5 -cvclopentadienyl)silane titanium dichloride 30 A. In a drybox, 5.0 g of (Me 4 C 5 SiMe 2 N t Bu)Ti(0'Pr) 2 (12.0 mmol) was dissolved in about 50 ml of hexane. Silicon tetrachloride (Aldrich, 99.999%, 2.9 ml, 25.3 mMol) was added by syringe. The color immediately darkened and a precipitate began to form. The reaction mixture was stirred overnight (about 18 hours). At the end of this time, the volatile materials were removed under reduced pressure to leave (Me^SiMeN^uJTiCl j as a yellow solid (4.35 g, 35 98% yield). The material was identified by comparison of its - NMR spectrum with spectra of the complex made by other routes. 1H NMR (C 6 D 6 ): 2.00 ppm (s, 6H), 1.99 ppm (s, 6H), 1.42 ppm (s, 9H), 0.42 ppm (s, 6H). B. In a drybox, 1.01g of (2.43 mmol) was dissolved in 25 ml of hexane in a Schlenck tube. BCI 3 (5.5 ml of a 1.0M solution in hexane) was added by syringe; the color became orange and the mixture turned cloudy. The mixture was stirred for three hours, then the volatile materials were removed under reduced pressure. The Schlenk tube was sealed and removed from the drybox to a Schlenk line, where it was heated to 70°C overnight under dynamic vacuum to remove the remaining volatile components. The next day, the Schlenk tube was returned to the drybox, where 0.74 g of orange/yellow powder was obtained (83%). The 1 H NMR spectrum of this material indicated it to be [(Me 4 C5)SiMe 2 N t Bu]TiCI 2 by comparison with the spectrum described in Example 2A. C In a drybox, 0.25 g of [(Me C 5 )SiMe 2 N t Bu]Ti(0'Pr) 2 (0.60 mmol) was dissolved in 20 ml of pentane. Et 2 AICI (1.2 ml of a 1.0 M solution in hexane) was added by syringe, and the color darkened immediately. The mixture was stirred for one hour, then the volatile materials were removed under reduced pressure to leave an oily yellow solid. The material was slurried in 3 ml of pentane and filtered to leave a bright yellow solid on the filter; this solid was washed with 2 ml of additional pentane and dried under vacuum. The 1 H NMR spectrum of this material indicated it to be extremely pure [(Me 4 C 5 )SiMe 2 N Bu]TiCI 2 by comparison with the spectrum described in Example 2A. Example 3: Preparation of (tert-butylamido)dimethyl(tetramethyl-n 5 -cvclopentadienyl)silane titanium dimethyl A. In a drybox, 0.26 g of (Me 4 C s SiMe 2 N t Bu)Ti(0'Pr) 2 (0.63 mMol) was dissolved in about 15 ml of hexane. Trimethylaluminum (Aldrich, 2M in hexane, 0.95 ml, 1.9 mmol) was added by syringe. The solution was heated to gentle reflux. After overnight (about 18 hours) reflux, the solution turned brown. The volatile materials were then removed under reduced pressure to leave (Me 4 C 5 SiMe 2 N t Bu)TiMe 2 as a pale brown solid. The material was identified by comparison of its 'H NMR spectrum with spectra of the complex made by other routes. 1 H NMR (C 6 D 6 ): 1.96 ppm (s, 6H), 1.85 ppm (s, 6H), 1.56 ppm (s, 9H), 0.51 ppm (s, 6H), 0.43 ppm (s, 6H). B. In a drybox, 0.255 g of [(Me 4 C 5 )SiMe 2 N t Bu]Ti(O i Pr) 2 (0.614 mmol) was dissolved in 20 ml of ether. Methyl lithium (1.75 ml of a 1.4M solution in ether) was added by syringe. The mixture was stirred overnight. At the end of this time, the solution was pale brown with a lightly colored precipitate. The volatile materials were removed under reduced pressure to leave a pale solid. The residue was extracted with pentane (20 ml), filtered, and dried under vacuum to leave an off-white crystalline solid. The 1 H NMR spectrum of this material indicated it to be primarily [(Me 4 C5)SiMe 2 N Bu]TiMe2; small peaks from [(Me 4 C 5 )SiMe 2 N t Bu](Me)O i Pr and LiO'Pr were also observed. C. In a drybox, 1.00 g of [(Me 4 C 5 )SiMe 2 NtBu]Ti(0'Pr) 2 (2.41 mmol) was dissolved in 20 ml of hexane. Trimethyl aluminum (3.0 ml of a 2.0 M solution in hexane) was added by syringe; the solution color darkened slightly. The mixture was heated to a gentle reflux with stirring overnight. At the end of this time, the solution was pale brown. The volatile materials were removed under reduced pressure to leave an off-white crystalline solid (0.79 g, 100%). The 1 H NMR spectrum of this material indicated it to be extremely pure by comparison with the spectrum in described Example 3A. Example 4: Preparation of (tert-butylamido)dimethyl(tetramethyle--η 5 -cvclopentadienyl) silane titanium dibromide In a drybox, 4.75 g of SiBr 4 (13.7 mmol; Aldrich) was weighed into a 100 ml flask and dissolved in 25 ml of hexane. [(Me C 5 )SiMe 2 NtBu]Ti(0'Pr)2 (2.25 g, 6.0 mmol) was added, using 10 ml of hexane to wash the material into the flask. The mixture was heated to reflux with stirring for four hours; the color changed to bright orange and the mixture became cloudy. At the end of this time, the volatile materials were removed under reduced pressure to leave a sticky orange solid. The material was slurried in a small volume of pentane and filtered to leave a bright orange solid on the filter; this solid was dried under vacuum to give 1.2 g of product (44%). The H NMR spectrum of this material indicated it to be [(Me 4 C 5 )SiMe 2 N t Bu]TiBr 2 by comparison with previous spectra. !H NMR (CβDβ. δ): 2.10 (2H), 1.96 (2H), 1.50 (3H), 0.40 (2H).

Claims: CLAIMS : 1. A process for preparing a metal dihydrocarbyloxy coordination complex corresponding to the formula: Cp* M / (I ) (OR ) ; wherein: M is titanium.zirconium, or hafnium; Cp* is a cyciopentadienyl group bound in an η5 bonding mode to M or such a cyciopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Cp* to have a fused ring structure; Z is a divalent moiety comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally sulfur or oxygen, said moiety having up to 50 non¬ hydrogen atoms, and optionally Cp* and Z together form a fused ring system; Y is a) a divalent anionic ligand group comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, said Y being bonded to Z and M through said nitrogen, phosphorus, oxygen or sulfur, and optionally Y and Z together form a fused ring system, or b) a cyciopentadienyl group bound in a sigma bonding mode to Z and in an η 5 bonding mode to M or such a cyciopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Y to have a fused ring structure; and R independently each occurrence is a hydrocarbyl group having from 1 to 20 carbon atoms; the steps of the process comprising: contacting in the presence of an aprotic organic diluent a metal compound of the formula: M(OR) wherein M and R are as previously defined with a dianionic salt compound corresponding to the formula: (L +x ) (Cp*-Z-Y) "2 or ((LX) +» ) (Cp*-Z-Y) "2 r wherein: L is a metal of Group 1 or 2 of the Periodic Table of the Elements, X independently is chloro, bromo, or iodo, x and y are either 1 or 2 and the product of x and y equals 2, and Cp*, Z, and Y are as previously defined; to form the complex of formula (I). 2. A process according to Claim 1 wherein the metal dihydrocarbyloxy coordination complex of formula (I) corresponds to the formula: wherein R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms, or two R' groups together form a divalent derivative thereof; E is silicon or carbon; m is 1 or 2; and M and R are as previously defined; and wherein the metal compound of the formula: M(OR) is contacted with a dianionic salt compound corresponding to the formula: (L +x ) y (C 5 R' 4 -(ER' 2 )m-NR')- 2 or ((LX) + *) y (C 5 R' 4 -(ER' 2 ) m -NR')- 2 wherein L, R', E, X, x, y, and m are as previously defined. 3. A process according to Claim 1 wherein R each occurrence is independently selected from the group consisting of ethyl, isopropyl, n-butyl, and t-butyl. 4. A process according to Claim 1 wherein the metal compound of the formula: M(OR) 4 is selected from the group consisting of tetra(ethoxy)titanium, tetra(isopropoxy) titanium, tetra(n-butoxy) titanium. 5. A process according to Claim 1 wherein the dianionic salt compound corresponds to the formula: ((MgCI) + ) 2 (Cp*-Z-Y)- 2 , or (Li+) 2 (Cp * -Z-YR wherein Cp*, Z, and Y are as previously defined. 6. A process according to Claim 1 wherein the aprotic organic diluent is an aliphatic or cycloaliphatic hydrocarbon solvent having from 5 to 10 carbon atoms. 7. A process according to Claim 1 wherein the process is conducted at a temperature between 0°C and 100°C. 8. A process for preparing a metal dihydrocarbyl coordination complex corresponding to the formula: (R" wherein: M is titanium, zirconium, or hafnium; Cp* is a cyciopentadienyl group bound in an η5 bonding mode to M or such a cyciopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Cp* to have a fused ring structure; Z is a divalent moiety comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally sulfur or oxygen, said moiety having up to 50 non¬ hydrogen atoms, and optionally Cp* and Z together form a fused ring system; Y is a) a divalent anionic ligand group comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, said Y being bonded to Z and M through said nitrogen, phosphorus, oxygen or sulfur, and optionally Y and Z together form a fused ring system, or b) a cyciopentadienyl group bound in a sigma bonding mode to Z and in an η 5 bonding mode to M or such a cyciopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Y to have a fused ring structure; and R"' independently each occurrence is a hydrocarbyl group, containing from 1 to 20 carbon atoms; the process comprising contacting in the presence of an aprotic organic diluent a metal coordination complex of formula: Cp* M / (I ) (OR ) ; wherein R independently each occurrence is a hydrocarbyl group having from 1 to 20 carbon atoms and Cp*, Z, Y, M, are as previously defined; with a hydrocarbylation agent comprising a group 1, 2, 12 or 13 metal or metal derivative and at least one hydrocarbyl group R"', to form the metal dihydrocarbyl coordination complex of formula (II). 9. A process according to Claim 8 wherein a metal dihydrocarbyl coordination complex corresponding to the formula: wherein R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms, or two R' groups together form a divalent derivative thereof; E is silicon or carbon; m is 1 or 2; and M and R"' are as previously defined; is prepared by contacting a metal dihydrocarbyloxy coordination complex corresponding to the formula: wherein: M, R', E, R, and m are as previously defined; with the hydrocarbylation agent. 10. A process according to Claim 8 wherein the metal coordination complex corresponding to formula (I) is prepared by contacting in the presence of an aprotic organic diluent a metal compound of the formula: M(OR) 4 wherein M and R are as previously defined with a dianionic salt compound corresponding to the formula: (L +x ) y (Cp*-Z-Y)- 2 or ((LX) +x ) y (Cp*-Z-Y)- 2 wherein: L is a metal of Group 1 or 2 of the Periodic Table of the Elements, X independently is chloro, bromo, or iodo, x and y are either 1 or 2 and the product of x and y equals 2, and Cp*, Z, and Y are as previously defined; optionally followed by recovering the complex corresponding to formula (I). 11. A process according to Claim 8 wherein R each occurrence is independently selected from the group consisting of ethyl, isopropyl, n-butyl, and t-butyl. 12. A process according to Claim 8 wherein R"' is a methyl, benzyl, or neopentyi group. 13. A process according to Claim 8 wherein the hydrocarbylation agent is selected from the group consisting of R"'Li, R'" 2 Mg, R"'MgX", R"' 3 AI, and R"'-substituted aluminoxanes, wherein X" is halogen. 14. A process according to Claim 13 wherein the hydrocarbylation agent is trimethylaluminum. 15. A process according to Claim 8 wherein the aprotic organic diluent comprises an aliphatic or cycloaliphatic hydrocarbon solvent having from 5 to 10 carbon atoms. 16. A process according to Claim 8 wherein the process is conducted at a temperature between 0 and 100°C. 17. A process for preparing a metal dihalide coordination complex corresponding to the formula: Z Cp* _ M (in ) (X ' ) 2 wherein: M is titanium, zirconium, or hafnium; Cp* is a cyciopentadienyl group bound in an η 5 bonding mode to M or such a cyciopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, cyano, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Cp* to have a fused ring structure; Z is a divalent moiety comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally sulfur or oxygen, said moiety having up to 50 non¬ hydrogen atoms, and optionally Cp* and Z together form a fused ring system; Y is a) a divalent anionic ligand group comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, said Y being bonded to Z and M through said nitrogen, phosphorus, oxygen or sulfur, and optionally Y and Z together form a fused ring system, or b) a cyciopentadienyl group bound in a sigma bonding mode to Z and in an η 5 bonding mode to M or such a cyciopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, amino, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Y to have a fused ring structure; and X' independently each occurrence is a halo group; the process comprising contacting in the presence of an aprotic organic diluent a metal coordination complex of formula: Z Cp* M"^ (I ) \ (OR ) 2 wherein R independently each occurrence is a hydrocarbyl group having from 1 to 20 carbon atoms and Cp*, Z, Y, M, are as previously defined; with a halogenation agent comprising at least a member of Group 13 or 14 of the Periodic Table of the Elements and at least one halo group X', to form the metal dihalide coordination complex of formula (III). 18. A process according to Claim 17 wherein a metal dihalide coordination complex corresponding to the formula: wherein R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halo and combinations thereof having up to 20 non-hydrogen atoms, or two R' groups together form a divalent derivative thereof; E is silicon or carbon; m is 1 or 2; and M and X' are as previously defined; is prepared by contacting a metal dihydrocarbyloxy coordination complex corresponding to the formula: wherein: M, R', E, R, and m are as previously defined; with the halogenation agent. 19. A process according to Claim 17 wherein the metal coordination complex corresponding to formula (I) is prepared by contacting in the presence of an aprotic organic diluent a metal compound of the formula: M(OR) 4 wherein M and R are as previously defined with a dianionic salt compound corresponding to the formula: (L +x ) y (Cp*-Z-Y) "2 or ((LX) +x ) y (Cp*-Z-Y)- 2 wherein: L is a metal of Group 1 or 2 of the Periodic Table of the Elements, X independently is chloro, bromo, or iodo, x and y are either 1 or 2 and the product of x and y equals 2, and Cp*, Z, and Y are as previously defined; optionally followed by recovering the complex corresponding to formula (I). 20. A process according to Claim 17 wherein R each occurrence is independently selected from the group consisting of ethyl, isopropyl, n-butyl, and t-butyl. 21. A process according to Claim 17 wherein X' is chloro. 22. A process according to Claim 17 wherein the halogenation agent is selected from the group consisting of silicon chlorides, boron chlorides and alkyl aluminum chlorides. 23. A process according to Claim 17 wherein the aprotic organic diluent comprises an aliphatic or cycloaliphatic hydrocarbon solvent having from 5 to 10 carbon atoms. 24. A process according to Claim 17 wherein the process is conducted at a temperature of between 0°C and 100°C.

Inventors: KOLTHAMMER BRIAN W S, ROSEN ROBERT K, KOLTHAMMER, BRIAN, W., S., ROSEN, ROBERT, K.
Applicants: DOW CHEMICAL CO, KOLTHAMMER BRIAN W S, ROSEN ROBERT K, KOLTHAMMER, BRIAN, W., S., ROSEN, ROBERT, K., THE DOW CHEMICAL COMPANY
Application year: 1995
Main classification: C07F19
IPC codes: C07F7, C07F17, C08F4, C08F10