MXPA96002890A - Synthesis of ciclopentadienilo metal coordination complexes from oxides dehidrocarbilo de me - Google Patents

Abstract

The present invention relates to a process for the preparation of a metal dihydrocarbyl coordination complex corresponding to formula II: wherein: M is titanium, Cp * is a cyclopentadienyl group, or a substituted cyclopentadienyl group, Z is a bivalent moiety comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally sulfur and oxygen, this fraction having up to 50 non-hydrogen atoms, and optionally Cp * and Z together forming a fused ring system; is a) a bivalent anionic ligand group comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, Y being linked 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 cyclopentadienyl group, R "independently in each presentation, is a hydrocarbyl group, comprising the process of contacting, n the presence of an aprotic organic diluent, a metal coordination complex of the formula I: wherein R, independently in each presentation, is a hydrocarbyl group having from 1 to 20 carbon atoms, and Cp *, Z, Y, M, are as defined for formula (II), with a hydrocarbylating agent comprising a metal or a metal derivative of group 1, 2, 12 or 13 and at least one hydrocarbyl group of metal of the formula (I)

Description

S NTESIS OF CYLOPENTADIENYL METAL COORDINATION COMPOUNDS FROM HYDROCARBON OXIDES OF METAL The present invention relates to a process for the preparation of certain bridged mono- and bis-cyclopentadienyl metal dihydrocarbyloxy coordination complexes, starting from metal hydrocarbyl oxide compounds. The present invention also relates to a process for the preparation of bridged mono and bis-cyclopentadienyl dihydrocarbyl metal coordination complexes, and to a process for the preparation of bridged mono- and bis-cyclopentadienyl metal dihalide coordination complexes , both starting from the corresponding bridged mono- or bis-cyclopentadienyl metal dihydrocarbyloxy coordination complexes. The 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 "Metall omplexe mit verbrueckten per etilierten Cyclopentadienylliganden "by P. Jutzi and R. Dickbreder, Chem.Ber. 119. 1750-1754 (1986), describes the synthesis of bis (cyclospentadienyl permethylated) titanium dichlorides bridged with dimethylsilandiyl from the tetrahydrofuran (THF) adducts of titanium tetrachloride and bis (cyclopentadienyl permethylated) dianion derivatives bridged with di-ethylsilandiyl In "ansa-Metaene derivatives: XVII. Racemic and meso diastereoisomers of group IV metaene derivatives with symmetrically substituted, dimethylsilanediyl-bridged ligand frameworks. Crystal structure of R, S-Me2Si (3-t-Bu-MeC5H2) 2ZrCl2"by H. Wiesenfeldt et al., Journal of Organometallic Chemistry, 369 (1989) 359-370, describes the synthesis of bis (dichloride) complexes. substituted cyclopentadienyl) titanium bridged with dimethylsilandiyl from the tetrahydrofuran adducts of titanium trichloride and the bis (cyclopentadienyl substituted) dianion derivatives bridged with dimethylsilandiyl In "Synthesis and Complexation of Linked Cyclopentadienyl-Amido Ligands" by J. Okuda, Chem. Ber. 123. (1990) 1649-1651, describes the preparation of a complex of bridged mono (cyclopentadienyl) titanium dichloride complex from the tetrahydrofuran adduct of titanium tetrachloride and the dilithium salt of cic 1 open t ad i in i ur or of [(tertiary butyl amino) dimethylsilyl] (tertiary butyl).

Coordination complexes of bridged ono-cyclopentadienyl metal dihalides are also prepared in U.S. Patent No. USP 5,026,798 from titanium tetrachloride compounds or etheric adducts thereof, and dilithium salts of compounds of bridged mono-cyclopentadienyl ligand. In addition, European Patent Number EP-A-0,416,815 describes a process for the preparation of bridged mono-cyclopentadienyl metal dihalide coordination complexes starting from transition metal tetrahalide and a derivative of Group 1 or Grignard of the bridged mono-cyclopentadienyl ligand compounds. The aforementioned synthesis methods for preparing the bridged mono- and bis-cyclopentadienyl metal dihalide coordination complexes use metal tetrahalide compounds as starting materials, which are corrosive, toxic, and sensitive to air and moisture . In order to facilitate its handling, before the reaction step, the transition metal tetrahalide compound is typically converted to its ether adduct in a separate step with, for example, tetrahydrofuran or diethyl ether. This step of forming the adduct itself proceeds with difficulty, requiring low to very low temperatures and an inert atmosphere. The adduct is normally recovered before being reacted with the dianionic derivative of the ligand compound. The yield of the step or steps of formation of the adduct is less than quantitative. further, the reaction mixture of the transition metal tetrahalide compound and the dianionic derivative of the dotted cyclopentadienyl ligand compound requires a multi-step process, a laborious recovery and purification. Typically, after the reaction step, the solvent is removed, the product is redissolved by the addition of dichloromethane or toluene or a mixture thereof, the metal halide byproduct, typically lithium chloride, is removed by filtration, of the mixture, the solvent is removed at least partially, followed by redissolution of the solid product and crystallization of the product, optionally followed by one or more additional recrystallization procedures. Furthermore, it is known, from European Patents Nos. EP-A-0,416,815 and EP-A-0, 514, 828, the preparation of dotted mono-cyclopentadienyl metal dihalide coordination complexes, by reaction of the adduct of tetrahydrofuran of a transition metal trihalide compound, especially TiCl 3, with the dianionic derivative of the cyclopentadienyl ligand. The resulting complex is contacted with a non-interfering oxidizing agent, such as, for example, AgCl (European Patent Number EP-A-0,416,815), or with an organic halide, to elevate the oxidation state of the metal to form the desired dihalide complex. Apart from requiring an extra reaction step, say, the oxidation step, this process also starts from the transition metal trihalide or an etheric adduct thereof, which has the drawbacks mentioned above, and requires long times of reaction to prepare. Additionally, the complex resulting from the reaction between the ether adduct of the transition metal trihalide compound with the dianionic derivative of the cyclopentadienyl ligand, i.e., the cyclopentadienyl metal (III) monohalide coordination complex, is thermally unstable. Bridged mono-cyclopentadienyl dihydrocarbyl metal coordination complexes can be prepared by the hydrocarbylation of 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 European Patent Number EP-A-0,418,044, Example 3, and WO 92/00333. These preparation processes inherently have the drawbacks associated with the preparations of the dotted mono-cyclopentadienyl metal dihalide coordination complexes. In one aspect, the present invention relates to a process for the preparation of a metal dihydrocarbyloxy coordination complex corresponding to the formula: (OR) wherein: M is titanium, zirconium, or hafnium; Cp * is a cyclopentadienyl group bonded in a? 5 linking mode with M, or a cyclopentadienyl group substituted with from 1 to 4 substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halogen, hydrocarbyloxy, cyano, amino, and mixtures thereof, this substituent having up to 20 non-hydrogen atoms, or optionally, two substituents together cause Cp * to have a fused ring structure; Z is a bivalent moiety comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally sulfur or oxygen, having this fraction up to 50 atoms that are not hydrogen, and optionally Cp * and Z together form a fused ring system; Y is a) a bivalent anionic ligand group comprising nitrogen, phosphorus, oxygen, or sulfur, and having up to 20 non-hydrogen atoms, Y being linked with Z and M through said nitrogen, phosphorus, oxygen, or sulfur, and optionally Y and Z together form a fused anills system, or b) a cyclopentadienyl group linked in a 5 • sigma bond mode with Z and in a 5? linkage mode with M, or a cyclopentadienyl group substituted with 1 to 4 substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halogen, hydrocarbyloxy, cyano, amino, and mixtures thereof, this substituent having up to 20 non-hydrogen atoms, or optionally, two substituents together they make Y have a fused ring structure; and R, independently in each presentation, is a hydrocarbyl group having from 1 to 20 carbon atoms; 5 comprising the steps of the process: contacting, in the presence of an aprotic organic diluent, a metal compound of the formula: M (0R) 4 wherein M and R are as defined above, with a compound of dianion salt corresponding to the formula: 0 (L + x) and (Cp * -ZY) "2 or ((LX) + x) and (Cp * -ZY)" 2 where: L is a Group 1 metal or 2 of the Periodic Table of the Elements, X is independently chlorine, bromine, or iodine, 5 x and y are either 1 or 2, and the product of x and y is equal to 2, and Cp *, Z, and Y are as defined above, to form the complex of the formula (I) In another aspect, the present invention relates to a process for the preparation of a metal dihydrocarbyl coordination complex corresponding to the formula: Cp * Vi (II) \ (R, M) 2 wherein: M is titanium, zirconium, or hafnium; Cp * is a cyclopentadienyl group bonded in a? 5 linking mode with M, or a cyclopentadienyl group substituted with from 1 to 4 substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halogen, hydrocarbyloxy, cyano, amino, and mixtures thereof, this substituent having up to 20 non-hydrogen atoms, or optionally, two substituents together cause Cp * to have a fused ring structure; Z is a bivalent moiety comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally sulfur or oxygen, having this fraction up to 50 atoms that are not hydrogen, and optionally Cp * and Z together form a fused ring system; Y is a) a bivalent anionic ligand? Uo group comprising nitrogen, phosphorus, oxygen, or sulfur, and having up to 20 non-hydrogen atoms, being Y linked with Z and M through said nitrogen, phosphorus, oxygen , or sulfur, and optionally Y and Z together form a fused ring system, or b) a cyclopentadienyl group bonded in a sigma bond with Z mode and in a? 5 linkage mode with M, or a cyclopentadienyl group substituted with 1 to 4 substituents selected from the group consisting of hydrocarbyl, silyl, geryl, halogen, hydrocarbyloxy, cyano, amino, and mixtures thereof, this substituent having up to 20 non-hydrogen atoms, or optionally, two substituents together they cause Y to have a molten ring structure; and R "'independently in each presentation, is a hydrocarbyl group having from 1 to 20 carbon atoms, the process comprising contacting, in the presence of an aprotic organic diluent, a metal coordination complex of the formula: Cp * W (I) (0F). wherein R, independently in each presentation, is a hydrocarbyl group having from 1 to 20 carbon atoms, and Cp *, Z, Y, M, are as defined above; with a hydrocarbylating agent comprising a metal or a metal derivative of group 1, 2, 12, or 13, and at least one hydrocarbyl group R "', to form the hydrocarbyl coordination complex of metal of the formula (II) In yet another aspect, the present invention relates to a process for the preparation of a metal dihalide coordination complex corresponding to the formula: Cp * M- (III) (X ' wherein: M is titanium, zirconium, or hafnium; Cp * is a cyclopentadienyl group bonded in a? 5 linking mode with M, or a cyclopentadienyl group substituted with from 1 to 4 substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halogen, hydrocarbyloxy, cyano, amino, and mixtures thereof, this substituent having up to 20 non-hydrogen atoms, or optionally, two substituents together cause Cp * to have a fused ring structure; Z is a bivalent moiety comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally sulfur or oxygen, this fraction having up to 50 non-hydrogen atoms, and optionally Cp * and Z together form a cast ring system; Y is a) a bivalent anionic ligand group comprising nitrogen, phosphorus, oxygen, or sulfur, and having up to 20 non-hydrogen atoms, Y being linked with Z and M through said nitrogen, phosphorus, oxygen, or sulfur, and optionally Y and Z together form a fused ring system, or b) a cyclopentadienyl group bonded in a sigma bond with Z mode and in a? 5 linkage mode with M, or a cyclopentadienyl group substituted with 1 to 4 substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halogen, hydrocarbyloxy, amino, and mixtures thereof, this substituent having up to 20 non-hydrogen atoms, or optionally, two substituents together cause Y to have a cast ring structure; and X * independently in each presentation is a halogen group; the process comprising contacting, in the presence of an aprotic organic diluent, a metal coordination complex of the formula: Cp < MY OR) wherein R independently in each presentation, is a hydrocarbyl group having from 1 to 20 carbon atoms, and Cp *, Z, Y, M, are as defined above; with a halogenating agent comprising at least one member of Group 13 or 14 of the Periodic Table of the Elements, and at least one halogen group X1, to form the metal dihalide coordination complex of the formula (III). All references 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 Group or Groups reflected in this Periodic Table of the Elements, using the IUPAC system to number the Groups. Surprisingly, it has been discovered that two hydrocarbyloxy groups can be easily removed on the titanium, zirconium, or hafnium center (hereinafter referred to as Group 4 metal) by contacting the compound M (OR), where M and R are as defined above, with the dianionic salt compound, to give the complexes of the formulas (I), (la), 6 (Ib), on a high yield and in a high purity. This discovery was really surprising, since the transition metal-hydrocarbyloxy bonds are considered stronger bonds than the transition metal-halogen bonds, and therefore, the hydrocarbyloxy groups are considered less suitable leaving groups than the halogen groups. The metal hydrocarbyloxy compounds of Group 4 starting, typically tetraisopropoxide, tetra-n-butoxide, and titanium tetra-t-butoxide, are non-viscous liquids, only moderately air-sensitive, commercially available, and readily soluble in hydrocarbons, compared to corrosive group IV metal tetras, sensitive to the air, and difficult to handle. This new process typically provides the complexes of formulas (I), (a), and (Ib) in yields of 90 percent and higher. The product complexes can be easily isolated in a high purity by filtration. In the present process, the bridged mono- or bis- (cyclopentadienyl) metal dihydrocarbyloxy coordination complexes of the formulas (I), (a), or (Ib), are prepared by contacting a metal tetrahydrocarbyloxy compound of Group 4 of the formula M (OR) 4, wherein M and R are as defined above, with a dianionic salt compound. The preferred dianionic salt is a double Group 1 metal derivative, or a Grignard derivative (Group 2 metal monohalide) double of the -Cp * -ZY- fraction, the anionic fillers formally residing on the Cp * e groups. Y. In the relevant part of the formula for the dianionic salt compound, the metal derivative of double Group 1 corresponds to (L + X) y, where x is 1 and y is 2, and the double Grignard derivative corresponds to ((LX) + x) and where x is 1 and y is 2. In the dihydrocarbyloxy metal coordination complexes of the formula (I) M is titanium, zirconium, or hafnium, and R, independently in each presentation, is a hydrocarbyl group having from 1 to 20 carbon atoms, more preferably R in each presentation is independently selected from the group consisting of the alkyl, aryl, alkaryl, and aralkyl groups, and still more preferably from the alkyl groups that have 1 to 6 carbon atoms, and of the ary groups it, aralkyl, and alkaryl having from 6 to 10 carbon atoms, and more preferably, R in each presentation is independently selected from the group consisting of ethyl, isopropyl, normal butyl, and tertiary butyl. A neutral Lewis base, such as an ether or amine compound, may also be associated with the complex, if desired; however, this is generally not preferred. The term "substituted cyclopentadienyl" includes, but is not limited to, the indenyl, tetraindenyl, fluorenyl, tetrahydrofluorenyl, and octahydrofluorenyl groups. The generic formula (I) encompasses bridged monocyclopentadienyl metal dihydrocarbyloxy coordination complexes and bridged bis (cyclopentadienyl) metal dihydrocarbyloxy coordination complexes. Preferred bridged monocyclopentadienyl metal dihydrocarbyloxy coordination complexes of the formula (I) prepared in the present process include those having limited geometry. The term "limited geometry" as used herein, means that the metal atom in the metal coordination complex, and also in the catalyst resulting therefrom, is forced to a greater exposure of the active site of the catalyst, due to a ring-specific structure of a ligand group that includes the metal atom, wherein the metal is both bound to an adjacent covalent moiety and maintained in association with the delocalised p-linked cyclopentadienyl group through a linkage? or another link interaction-ü. It is understood that each respective bond between the metal atom and the constituent atoms of the p-linked fraction need not be equivalent. That is, the metal can be symmetrically or asymmetrically p-linked therewith.

The concept of limited geometry and ligand groups that induce a specific limitation is described in greater detail in U.S. Patent Application Serial Number 545,403, filed July 3, 1990 (corresponding to the Patent). European Patent Number EP-A-0, 416, 815), which is incorporated herein by reference. Suitable examples of the Z-moiety in the formula (I) include SiR * 2, CR * 2, SiR * 2Sir * 2, CR * 2CR * 2, CR * = CR *, CR * 2SiR * 2, GeR * 2, or BR *, wherein R * in each presentation 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 of the same, or two or more groups R * from Z or a group R * from Z, together with Y, form a fused ring system. Still more preferably, Y in formula (I) is -0-, -S-, -NR * -, PR * -. In a highly preferable manner, Y is a group containing nitrogen or phosphorus corresponding to the formula -N (R ') - or -P (R') -, that is, an amido or phosphido group, wherein R 'is as it is defined later in the present. More preferably, in the present process, a metal coordination dihydrocarbyloxy complex of the formula (I) corresponding to the formula is prepared: wherein R ', in each presentation, is independently selected from the group consisting of hydrogen, silyl , alkyl, aryl, germyl, cyano, halogen, and combinations thereof having up to 20 non-hydrogen atoms, or two R 'groups together form a bivalent derivative thereof; E is silicon or carbon; m is 1 or 2; and M and R are as defined above; and wherein the metal compound of the formula: M (0R) 4 is contacted with a corresponding dianionic salt compound of the formula: (L + x) and (C5R'4- (ER'2) m-NR ') ~ 2ó ((LX) + x) and (C5R'4- (ER'2) m-NR1) "2 where L, R1, E, X, x, y, and m are as defined above. note that when a substituent, such as R ', on a cyclopentadienyl group, is hydrogen, halogen, or cyano, two of these substituents can not together form a bivalent derivative thereof, nor cause the groups to have a fused ring structure. In the complexes of the formula (la), M is preferably titanium, and preferably R, independently in each presentation, is the alkyl, aryl, aralkyl, and alkaryl groups, more preferably it is selected from an alkyl group having from 1 to 6 carbon atoms, and from the aryl, aralkyl, and alkaryl groups having from 6 to 10 carbon atoms, and still more preferably R is alkyl of 1 to 4 carbon atoms, and ally ethyl, isopropyl, normal butyl, or tertiary butyl. Examples of the most highly preferred metal dihydrocarbyloxy coordination compounds include those compounds wherein R 'on the amido group is methyl, ethyl, propyl, butyl, pentyl, hexyl, and isomers of these alkyl, norbornyl, benzyl radicals , phenyl, etcetera; the cyclopentadienyl group is cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl, octahydrofluorenyl, etc.; R 'on the above cyclopentadienyl groups, in each presentation, is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, and isomers of these alkyl, norbornyl, benzyl, phenyl, etc. radicals; and R is ethyl, isopropyl, normal butyl, or tertiary butyl. Specific highly preferred compounds include: titanium dioxide (tertiary butyl amido) (tetramethyl-? 5- cyclopentadienyl) -1, 2-ethanediyl, titanium di-isopropoxide (tertiary butyl amido) (tetramethyl-? 5-) cyclopentadienyl) -1, 2-ethanediyl, normal titanium di-butoxide (tertiary butyl io-amido) (tetramethyl-? 5-cyclopentadienyl) -1, 2-ethanediyl, titanium di-ethoxide (tertiary butyl-amido) (tetramethyl) l-? 5-cyclopentadienyl) dimethylsilane, titanium di-isopropoxide (tertiary butyl amido) (tetramethyl-? 5-cyclopentadienyl) di ethylsilane, normal titanium di-butoxide (tertiary butyl io-amido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, titanium di-ethoxide (methylated) ( tetramethyl-? 5-cyclopentadienyl) dimethylsilane, titanium di-isopropoxide (methylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, normal titanium di-butoxide (methylamido) (tetramethyl-? 5 -cyclopentadienyl) dimethylsilane, di-ethoxide titanium (feni lamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, titanium di-isopropoxide (phenylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, normal titanium di-butoxide (phenylamido) (tetramethyl-? 5 -cyclopentadienil) ) dimethylsilane, titanium dioxide (benzylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, titanium di-isopropoxide (benzylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, normal di-butoxide t a n i o (be n c i l am i d o) (t e t r ame t i l -? 5-cyclopentadienyl) dimethylsilane, titanium di-ethoxide (tertiary butyl-amido) (5-cyclopentadienyl) -1, 2-ethanediyl, titanium di-isopropoxide (tertiary butyl amido) (5-cyclopentadienyl) -1, 2-ethanediyl, normal titanium di-butoxide (tertiary-butyl amido) (? 5-cyclopentadienyl) -1, 2-ethanediyl, titanium di-ethoxide (tertiary butyl-amido) (? 5-cyclopentadienyl) dimethylsulinic, di-isopropoxide titanium (but-tertiary-amido) (? 5-cyclopentadienyl) dimethylsilane, normal titanium di-butoxide (but-tertiary-butylated) (? 5 -cyclopentadienyl) dimethylsilane, titanium di-ethoxide (methylamido) (? 5) -cyclopentadienyl) dimethylsilane, titanium di-isopropoxide (methylamido) (? 5-cyclopentadienyl) dimethylsilane, normal titanium di-butoxide (but-tertiary-amido) (? 5 -cyclopentadienyl) dimethylsilane, tertiary-butyl di-ethoxide indenyldimethylsilane, d titanium (tertiary butyl-amido) indenyldimethylsilane, normal titanium (tertiary butyl-amido) indenyldimethylsilane, titanium (benzylamido) indenyldi-ethylsilane di-ethoxide, and titanium (benzylamido) indenyldimethylsilane di-isopropoxide.

According to another preferred embodiment of the present process, a metal coordination complex of the formula (I) corresponding to the formula is prepared: wherein: R ', in each presentation, is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halogen, and combinations thereof having up to 20 non-hydrogen atoms, or two R 'groups together form a bivalent derivative thereof; E is silicon or carbon; R ", independently in each presentation, is hydrogen or a group selected from silyl, hydrocarbyl, and combinations thereof, this R" having up to 30 carbon or silicon atoms; m is from 1 to 8; and M and R are as defined above; and wherein the metal compound of the formula: M (O) 4 is contacted with a corresponding dianionic salt compound of the formula: (L + x) and (C5R'4- (ER "2) m-C5R '4r2 or ((LX + x) and (C5R'4- (ER "2) m-C5R'4) -2 where L, R', E, R", X, m, x, and y are as The exemplary metal complexes of the bridged bis-cyclopentadienyl metal dihydrocarbyloxy coordination complexes include those complexes of the formula (Ib) wherein E is silicon or carbon, R "independently in each presentation, is hydrogen or a group selected from silyl, hydrocarbyl, and combinations thereof, having this R "up to 30 carbon or silicon atoms, and m is from 1 to 8. Preferably, R", independently in each presentation, is methyl, benzyl, tertiary butyl, or phenyl These bridged bis (cyclopentadienyl) structures are especially suitable for use as catalysts, or precursors thereof, for the preparation of polymers having a stereoregular molecular structure. In this capacity, it is preferred that the complex be non-symmetric or have a stereorigid chiral structure. Examples of the first type are compounds possessing different delocalized p-linked systems such as a cyclopentadienyl group, and an indenyl group. Examples of the chiral structures include the bis-indenyl complexes. Examples of bridged bis (cyclopentadienyl) metal dihydrocarbyloxy complexes of the formula (Ib) are those in which the bridged ligand group is: dimethylsilyl-bis-cyclopentadienyl, dimethylsilyl-bis-tetramethylcyclopentadienyl, dimethylsilyl-bis-indenyl , isopropy lidene-cyclopentadieni 1-fluoreni lo, 2,2'-biphenyldiylbis (3,4-dimethyl-l-cyclopentadienyl), and 6,6-dimethyl-2-2'-bifeniIbis (3,4-dimethyl-l- cyclopentadienyl). In a preferred embodiment, the fraction ((LX) + x) in the dianionic salt compound corresponds to ((MgCl) +) 2. In another preferred embodiment, the fraction (L + x) 2 in the dianion salt corresponds to (Li +) 2. The use of the first dianionic salt compound in the present process gives as a by-product MgCl (OR), which can be easily separated from the desired product. The molar ratio of the dianionic salt compound to the metal dihydrocarbyloxy compound M (0R) can vary widely. Although improved process can be obtained with molar ratios of the dianion salt compound to the metal compound 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 in proportions 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 these 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 isoparaffin hydrocarbons available from Exxon Chemical Inc.), isooctane, cyclohexane, and methylcyclohexane. Carrying out the reaction in a hydrocarbon solvent has the advantage that the product of the dihydrocarbyloxy complexes of the formulas (I), (a), and (Ib) is soluble, while the by-product L-OR or LX- OR generally it is not. The products desired in this way can be easily recovered, if desired, by filtration or other liquid-solid separation methods. By subjecting the liquid thus obtained to a separation step to remove the volatile solvent, a highly pure product is obtained. The temperature at which the process is conducted is not critical, but is preferably lower than the boiling point of the diluent. Preferred temperatures are from 0 ° C to 100 ° C, more preferably from 10 ° C to 80 ° C, and most preferably from 20 ° C to 60 ° C. In general, the reactants are contacted under an inert atmosphere for a time from several minutes to several days. Preferably the presence of oxygen and moisture is avoided. The reagents can be added in any order. Agitation may be employed if desired. In accordance with a further aspect, the present invention provides a process for the preparation of bridged mono- or bis-cyclopentadienyl dihydrocarbyl metal coordination complexes of the formulas (II), (Ha), and (Hb), putting contacting a corresponding metal dihydrocarbyloxy coordination complex of the formula (I), (a), or (Ib) obtainable as described hereinabove, with a hydrocarbylation agent comprising a metal or a derivative of metal of Group 1, 2, 12, or 13, and at least one hydrocarbyl group R "'to form the dihydrocarbyl metal coordination complex of formula (II), (Ha), or (Hb). Surprisingly, it has been found that the hydrocarbyloxy complexes of the formulas (I), (la), and (Ib), are stable compounds that can be easily converted to the corresponding dihydrocarbyl compounds of the formulas (II), (Ha ), or (Ilb) in high yields The present hydrocarbylation process, especially in combination with the process for the preparation of metal dihydrocarbyloxy coordination complexes of the formulas (I), (a) or (Ib) as described hereinabove, makes It is possible that the valuable complexes of formulas (II), (Ha), or (Ilb) are prepared in high global yields, compared with a process starting from metal tetrahalide compounds. In a preferred embodiment, a metal dihydrocarbyl coordination complex corresponding to the formula is prepared: wherein R1, in each presentation, is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halogen, and combinations thereof having up to 20 non-hydrogen atoms, or two R 'groups together form a bivalent derivative thereof; E is silicon or carbon; m is 1 or 2; and M and R "• are as defined above; by contacting a metal dihydrocarbyloxy coordination complex corresponding to the formula: R wherein: M, R ', E, R, and m are as defined above; with the hydrocarbylation agent. In another preferred embodiment, a metal dihydrocarbyl coordination complex corresponding to the formula is prepared: ( (Hb) wherein R ', in each presentation, is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halogen, and combinations thereof having up to 20 atoms which are not hydrogen, or two R 'groups together form a bivalent derivative thereof; E is silicon or carbon; R ", independently in each presentation, is hydrogen or a group selected from silyl, hydrocarbyl, and combinations thereof, this R" having up to 30 carbon or silicon atoms; m is from 1 to 8; and M and R "* are as defined above, by contacting a metal dihydrocarbyloxy coordination complex corresponding to the formula: ( wherein R ', E, R ", M, R, and m are as defined above, with the hydrocarbylating agent In a further preferred embodiment, the metal dihydrocarbyloxy coordination complex of the formula (I), (la), or (Ib), used as the starting compound in the preparation of the complexes of formulas (II), (Ha), or (Hb), is prepared by contact, in the presence of an aprotic organic diluent, of a metal compound of the formula: M (OR) 4, wherein M and R are as defined above, with a salt compound dianionic corresponding to the formula: (L + x) and (Cp * -ZY) -2 or ((LX) + x) and (Cp * -ZY) _2 where: L is a metal of Group 1 or 2 of the Periodic Table of the Elements, X is independently chlorine, bromine, or iodine, x and y are either 1 or 2, and the product of x and y is equal to 2, and Cp *, Z, and Y are as defined above; optionally followed by recovery of the complex corresponding to formula (I). In the complexes of the formulas (I), (la), and (Ib), M is titanium, zirconium, or hafnium, and R independently in each presentation, is a hydrocarbyl group having from 1 to 20 carbon atoms, preferably R in each presentation is independently selected from the group consisting of alkyl groups, aryl, aralkyl, and alkaryl, more preferably in the alkyl groups having from 2 to 6 carbon atoms, and in the aryl, aralkyl, and alkaryl groups having from 6 to 10 carbon atoms, and most preferably R in each presentation is independently selected from the group consisting of ethyl, -. Isopropyl, normal butyl, and tertiary butyl. Preferred embodiments of the present process for preparing the complexes of formulas (I), (a), and (Ib) were illustrated hereinabove, and are incorporated herein by reference. The complexes of the formulas (I), (a), and (Ib) as obtained, can be recovered or purified, if desired, before proceeding with the hydrocarbylation step. The hydrocarbyl group R '"in the formulas (II), (Ha), and (Ilb), and present in the hydrocarbylating agent, generally has from 1 to 20 carbon atoms, and can be an aliphatic, cycloaliphatic hydrocarbon, or aromatic 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 of the aralkyl groups having from 7 to 10 carbon atoms. Most preferably, R "• is methyl, neopentyl, or benzyl The hydrocarbylating agent comprises a metal or a metal derivative of Group 1, 2, 12 or 13, and at least one hydrocarbyl group R" *. Suitable examples of the hydrocarbylation agent 5 include LiR "', MgR"' 2, MgR "'X" (wherein X "is halogen, preferably chlorine), A1R"' 3, and aluminoxane substituted by R "•. aluminoxanes substituted by R "'suitable preferably include alkyl aluminoxanes of > - "1 to 6 carbon atoms, especially methyl aluminoxane. -d Alkyl aluminoxanes are well known in the art, and methods for their preparation are illustrated in 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 hydrocarbylating agent is trialkyl aluminum, and most preferably trimethyl aluminum. Specific highly preferred complexes of the formula (Ha) include: titanium dimethyl (tertiary butyl-0 amido) (tetramethyl-? 5-cyclopentadienyl) -1, 2-ethanediyl, titanium dibenzyl (tertiary butyl amido) (tetramethyl) -? 5- cyclopentadienyl) -1, 2-ethanediyl, titanium dimethyl (tertiary butyl amido) (tetramethyl-5-cyclopentadienyl) dimethylsilane, titanium dibenzyl (tertiary butyl amido) (tetramethyl-5-cyclopentadienyl) dimethylsilane,. dimethyl titanium (methylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, titanium dibenzyl (methylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, dimethyl titanium (phenylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, dibenzyl titanium (phenylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, titanium dimethyl (benzylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, titanium dibenzyl (benzylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, titanium dimethyl ( tertiary-butyl butyl) (? 5-cyclopentadienyl) -1, 2-ethanediyl, titanium dibenzyl (tertiary-butyl amido) (? 5-cyclopentadienyl) -1, 2-ethanediyl, titanium dimethyl (tertiary-butyl amido) ( ? -cyclopentadienyl) dimethylsilane, titanium dibenzyl (tertiary butyl amido) (? 5-cyclopentadienyl) dimethylsilane, titanium dimethyl (methylamido) (? 5-cyclopentadienyl) dimethylsilane, dibenzyl or titanium (butyl tertiary-amido) (? 5 -cyclopentadienyl) tell me tilsilanic, titanium dimethyl (tertiary butyl amido) indenyldimethylsilane, titanium dibenzyl (tertiary butyl amido) indenyldimethylsilane, and titanium (benzylamido) indenyldimethylsilane dibenzyl. The molar ratio of the hydrocarbylating agent to the complex of the formulas (I), (la), and (Ib), can vary within wide limits, but is preferably between 0.1: 1 and 20: 1, more preferably between 0.5: 1 to 10: 1. Conveniently, an equivalent amount or a slight excess of R "'groups in the hydrocarbylating agent is used with respect to the metal hydrocarbyloxy compound of the formulas (I), (a), or (Ib), i.e. , a ratio of 2.0: 1 to 4.0: 1, more preferably 2.1: 1 to 3: 1. The temperature at which the hydrocarbylation step is conducted is not critical, but is preferably lower than the boiling point of the diluent aprotic organic The preferred temperatures are from 0 ° C to 100 ° C, more preferably from 10 ° C to 80 ° C. In general, the reagents are contacted under an inert atmosphere for a time from several minutes to several days. The reagents can be added in any order, stirring can be used if desired.In the present hydrocarbylation step, an aprotic organic diluent is used.Preferably, diluents are used wherein the complexes of the formulas (I), (the) , and (Ib) are easily soluble, optionally with heating. Suitable examples of these solvents are ethers and hydrocarbons. Preferably, the solvent is a hydrocarbon, conveniently 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 the formulas (I), (a), and (Ib) are soluble and non-volatile, while the by-product of the oxides of The hydrocarbyl of the metal or metal derivative of Group 1, 2, 12 or 13 are often insoluble or volatile, especially when R is lower alkyl, such as alkyl of 1 to 4 carbon atoms. Accordingly, byproducts LiOR and Mg (OR) R "• are generally not soluble in hydrocarbons when R is a lower alkyl, and can be easily removed from the desired hydrocarbyl product by filtration, decantation, or other liquid separation method. When the liquid thus obtained is subjected to a separation step to remove the volatile solvent, a highly pure product can be obtained.However, the by-product formed when the highly preferred trimethyl aluminum is used as the hydrocarbylation agent, comprises an oxide The volatile aluminum hydrocarbyl hydrocarbyl This byproduct can be removed from the desired product by applying a vacuum to remove both the byproduct and the solvent / diluent in one step.According to another aspect, the present invention provides a process for the preparation of coordination complexes of dihalide of mono- or bis- (cyclopentadienyl) metal of the formulas (III), (Illa), 6 (IHb), by contacting a corresponding dihydrocarbyloxy metal coordination complex of the formula (I), (a), or (Ib), which may be obtained as described hereinabove, with a halogenating agent comprising an element of Group 13 or 14 or a derivative thereof, and at least one Halogen group X * to form the metal dihalide coordination complex of the formulas (III), (Illa), or (IHb). Surprisingly, it has been found that the dihydrocarbyloxy complexes of the formulas (I), (a), or (Ib), are stable compounds that can be easily converted to the corresponding dihalide compounds of the formulas (III), (Illa), or (IHb) in high yields and purity. The present halogenation process, especially in combination with the process for the preparation of the metal dihydrocarbyloxy coordination complexes of the formulas (I), (a), or (Ib) as described hereinabove, makes it possible for Complexes of the formulas (III), (Illa), or (IHb) are prepared in high yields, comparing with a process starting from metal tetrahalide compounds.

In a preferred embodiment, a metal dihalide coordination complex corresponding to the formula (Illa) is prepared: wherein R ', in each presentation, is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halogen, and combinations thereof having up to 20 non-hydrogen atoms, or two R 'groups together form a bivalent derivative thereof; E is silicon or carbon; m is 1 or 2; and M and X 'are as defined above; by contacting a metal dihydrocarbyloxy coordination complex corresponding to the formula: wherein: M, R ', E, R, and m are as defined above; with the halogenation agent. In another preferred embodiment, a metal dihalide coordination complex corresponding to formula (IHb) is prepared: wherein R ', in each presentation, is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halogen, and combinations thereof having up to 20 non-hydrogen atoms, or two R * groups together form a bivalent derivative thereof; E is silicon or carbon; R "independently in each presentation, is hydrogen or a group selected from silyl, hydrocarbyl, and combinations thereof, this R" having up to 30 carbon or silicon atoms; m is from 1 to 8; and M and X 'are as defined above; by contacting a metal dihydrocarbyloxy coordination complex corresponding to the formula: wherein R ', E, R ", M, R, and m are as defined above, with the halogenation agent, In a further preferred embodiment, the metal dihydroscarbyloxy coordination complex of the formulas (I), (the ), or (Ib), used as the starting compound in the preparation of the complexes of the formulas (III), (Illa), or (Hlb), is prepared by contact, in the presence of an aprotic organic diluent, of a metal compound of the formula: M (OR) 4, wherein M and R are as defined above, with a dianionic salt compound corresponding to the formula: (L + x) and (Cp * -ZY) -2 or ((LX) + x) y (Cp * -ZY) -2 wherein: L is a metal of Group 1 or 2 of the Periodic Table of the Elements, X is independently chlorine, bromine, or iodine. x and y are either 1 or 2, and the product of x and y is equal to 2, and Cp *, Z and Y are as defined above; optionally followed by recovery of the complex corresponding to formula (I). In the complexes of the formulas (I), (la), and (Ib), M is titanium, zirconium, or hafnium and R, independently in each presentation, is a hydrocarbyl group having from 1 to 20 carbon atoms, preferably R, in each presentation, is independently selected from the group consisting of the groups alkyl, aryl, aralkyl, and alkaryl, more preferably in alkyl groups having from 2 to 6 carbon atoms, and in the aryl, aralkyl, and alkaryl groups there are 6 to 10 carbon atoms, and more preferably R, in each presentation, it is independently selected from an alkyl of 1 to 4 carbon atoms, especially from the group consisting of ethyl, isopropyl, normal butyl, and tertiary butyl. Preferred embodiments of the present process for preparing the complexes of formulas (I), (a), and (Ib), are illustrated hereinabove, and are incorporated herein by reference. The complexes of the formulas (I), (la) and (Ib), as obtained, can be recovered or purified, if desired, before proceeding with the halogenation process. The halogen group X * in the formulas (III), (Illa), and (IHb), and in the halogenating agent, may be chlorine, bromine, or iodine, but is preferably chlorine. The halogenating agent comprises an element of the group 13 or 14 or a derivative thereof, and at least one halogen group X. Suitable examples of the halogenating agent include the halides, preferably boron, aluminum, and silicon chlorides, and the acetyl halides, such as acetyl bromide and acetyl chloride. Preferably, the halogenating agent is selected from the group consisting of silicon tetrachloride, boron trichloride, and alkyl aluminum chlorides, more preferably dialkyl aluminum chlorides, such as diethyl aluminum chloride. The most preferred halogenating agents are silicon tetrachloride and boron trichloride. Specific highly preferred complexes of the formula IHb include: titanium dichloride (tertiary butyl amide) (tetramethyl-? 5-cyclopentadienyl) -1, 2-ethanediyl, tertiary butyl dichloride (tetramethyl-? 5-cyclopentadienyl) ) dimethylsilane, titanium dichloride 5 (methylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, titanium dichloride (phenylamido) (tetramethyl-? 5- cyclopentadienyl) dimethylsilane, titanium dichloride (benzylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, titanium dichloride (tertiary butyl amide) (? 5-C> cyclopentadienyl) -1, 2-ethanediyl, titanium dichloride (tertiary butyl-amido) (? 5-cyclopentadienyl) dimethylsilane, titanium dichloride (methylamides) ) (? 5- cyclopentadienyl) imethylsilane, and titanium dichloride (tertiary butyl amido) indenyldimethylsilane. The molar ratio of the halogenating agent to the complex of the formulas (I), (la), and (Ib) can vary between wide limits, but is preferably between 0.1: 1 and 20: 1, more preferably between 0.5: 1 and 10: 1. In a convenient way, an equivalent or a slight stoichiometric excess amount of the halogenating agent is used with respect to the metal dihydrocarbyloxy compound of the formula (I), (a), or (Ib), ie, a ratio of 2.0: 1 to 4.0: 1, more preferably from 2.1: 1 to 3: 1. The temperature at which the halogenation step is conducted is not critical, but is preferably lower than the boiling point of the diluent. Preferred temperatures are from 0 ° C to 100 ° C, more preferably from 10 ° C to 80 ° C. In general, the reactants are contacted under an inert atmosphere for a time from several minutes to several days. Reagents can be added in any order. Agitation may be used if desired. In the present step of halogenation, a ^ - aprotic organic diluent. Preferably, 0 diluents are used wherein the complexes of formulas (I), (a), and (Ib) are readily soluble, optionally with heating. Suitable examples of these solvents are ethers and hydrocarbons. Preferably, the solvent is a hydrocarbon, conveniently 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, the isolation of the desired complexes can take place as required by the by-products. The removal of volatiles, such as the solvent, is preferably carried out by vacuum distillation at elevated temperatures. When silicon tetrachloride is used as the halogenating agent, the by-product formed comprises a hydrocarbyloxy silicon chloride. The by-products containing lower alkyls in the hydrocarbyloxy portion, especially the alkyls of 1 to 4 carbon atoms, can be volatile. These volatile by-products can be easily removed from the desired product by the use of vacuum distillation. Generally, highly pure products are obtained, in comparison with the methods of the prior art, which require extensive filtration and recrystallization steps. The compounds prepared with the processes according to the present invention, ie the complexes of the formulas (I), (a), (Ib), (II), (Ha), (Hb), (III), ( Illa), and (IHb) can be used as components of catalyst systems, or precursors thereof, useful in the addition polymerization processes. In a process for the preparation of a polymer of one or more addition polymerizable monomers, a catalyst comprising a metal coordination complex of any of the aforementioned formulas, and an activating cocatalyst, is contacted with one or more monomers polymerizable by addition, under addition polymerization conditions. Suitable activating cocatalysts are, for example, as described in U.S. Patent Applications Nos. 545,403, filed July 3, 1990 (corresponding to European Patent Number EP-A-0,416,815) and 817,202, filed on January 6, 1992 (corresponding to WO-A-92/10360), which are incorporated herein by reference. Preferred examples of activating cocatalysts include alumoxanes, conveniently methyl alumoxane, borane tris (perfluorophenyl), and borate tetra (perfluorophenyls). The "addition polymerizable monomers" include, for example, ethylenically unsaturated monomers, conjugated or non-conjugated dienes, polyenes, and the like. Preferred monomers include the α-olefins of 2 to 10 carbon atoms, especially ethylene, propylene, isobutylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. Other preferred monomers include styrene, substituted by halogen or by alkyl, benzocyclobutane vinyl, 1,4-hexadiene, ethylidenorbornene, cyclopentene, and norbornene. Catalysts suitable for use in accordance with the present invention are prepared by combining the metal coordination complex of formulas (I), (II), or (III), and the activating cocatalyst compound in any order and from any properly. Preferably, the ratio of the coordination complex and the cocatalyst on a molar basis is from about 1: 1 to about 1: 10,000. Of course, it will be appreciated that the catalyst system can also be formed on site if the components thereof are added directly to the polymerization process, and a suitable solvent or diluent, including a condensed monomer, is used in said polymerization process. Suitable solvents include toluene, ethyl benzene, alkanes, and mixtures thereof. In certain cases, the catalysts can be isolated from the solution and can be retained under an inert atmosphere before being used. The components of the catalysts are sensitive to both moisture and oxygen, and must be handled and transferred in an inert atmosphere such as _. nitrogen, argon, or helium, or vacuum. The polymerization is conducted according to the known techniques for Ziegler-Natta or Kaminsky-Sinn type polymerizations. That is, the monomers and the catalyst are contacted at a temperature of -30 ° C to 250 ° C, at reduced, high, or atmospheric pressures. The polymerization is conducted under an inert atmosphere, which may be a mantle gas such as nitrogen, argon, hydrogen, ethylene, et cetera, or under vacuum. Additionally hydrogen can be used in the control of molecular weight through chain termination, as previously known in the art. The catalyst can be used as is, or can be supported on a suitable support such as alumina, MgCl 2, or silica, to provide a heterogeneous supported catalyst. If desired, a solvent can be employed. Suitable solvents include toluene, ethylbenzene, alkanes, and an excess of vinyl aromatic or olefinic monomer. The reaction may also be conducted under solution or paste conditions, in a suspension using a perfluorinated hydrocarbon or a similar liquid, in the gas phase, i.e., using a fluidized bed reactor, or in a solid phase powder. A catalytically effective amount of the present catalyst and cocatalyst is any amount that results in successful polymer formation. These amounts can be easily determined by routine experimentation by the expert. The preferred amounts of catalyst and cocatalyst are sufficient to provide an equivalent ratio of polymerization monomer by addition: catalyst, from 1 × 1010: 1 to 100: 1, preferably 1 × 10 8: 1 to 500: 1, more preferably 1 5 x 106: 1 to 1000: 1. The cocatalyst is generally used 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 should be understood that the metal complex can undergo several transformations or form intermediate species before and during the course of the polymerization. The resulting polymer product is recovered by filtration or other suitable technique. Additives and auxiliaries can be incorporated into the polymers of the present invention, in order to provide desirable characteristics. Suitable additives include pigments, ultraviolet 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 should not be construed as limiting.

Example 1; Preparation of titanium diisopropoxide (tertiary butyl amido) dimethyl (tetramethyl-? 5-cyclopentadienyl) silane.

In a dry box, 24.95 grams of titanium tetraisopropoxide (Ti (01Pr) 4) (Aldrich Chemical Company) (88 millimoles) was dissolved in approximately 200 milliliters of hexane. 58 grams of di (chloromagnesium) (tertiary butyl amido) -dimethyl (tetramethylcyclopentadienyl) silane complex complexed with dimethoxyethane, [Me4C5SiMe2NtBu] [MgCl] 2 (DME) n (effective molecular weight by titration: approximately 629 grams / mol; 92 millimoles) (prepared according to the following procedure: In an apparatus consisting of a 3-liter round bottom flask, which was equipped with a stirrer, a condenser, and a nitrogen inlet, 500 milliliters of toluene were charged, followed by 106 grams of Me4C5HSiMe2NHtBu, and then 380 milliliters of iPrMgCl 2.2 M in Et20.The mixture was then heated, and the ether was removed by distillation, and trapped in a condenser cooled to -78 [deg.] C. After 5 hours of After heating, the heater was turned off, and slowly 450 milliliters of dimethoxyethane (DME) was added to the hot stirred solution, resulting in the precipitation of a white solid.The solution was allowed to cool to the At 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 grams (79 percent yield) of [Me4C5SiMe2NtBu] [MgCl] 2 (DME) n as a white solid were obtained.) To the flask, using approximately 50 milliliters of additional hexane. The mixture was stirred overnight at room temperature, then filtered through a fritted glass filter of medium porosity (porosity of 10 to 15 microns). The remaining solids on the frit were washed with additional hexane, until the washings were colorless. A yellow / orange solution was obtained, and the volatile materials were removed from this solution under reduced pressure to leave (Me4C5SiMe2NtBu) Ti (OxPr) 2 as a yellow crystalline solid in an essentially quantitative yield. 1 H NMR (C6D6): 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 titanium dichloride (tertiary butyl amido) dimethyl (tetramethyl-? 5-cyclopentadienyl) silane.

A. In a dry box, 5.0 grams of (Me4C5SiMe2NtBu) Ti (01Pr) 2 (12.0 mmol) in about 50 milliliters of hexane. Silicon tetrachloride (Aldrich, 99.999 percent, 2.9 milliliters, 25.3 mmol) was added with a syringe. The color darkened immediately, and a precipitate began to form. The reaction mixture was stirred overnight (approximately 18 hours). At the end of this time, the volatile materials were removed under reduced pressure to leave (Me4C5SiMeNtBu) TiCl2 as a yellow solid (4.35 grams, 98 percent yield). The material was identified by a comparison of its 1 H NMR spectrum with the spectra of the complex made by other routes. 1 H NMR (C6D6): 2.00 ppm (s, 6H), 1.99 ppm (s, 6H), 1.42 ppm (s, 9H), 0.42 ppm (s, 6H).

B. In a dry box, 1.01 grams of [Me4C5SiMe2NtBu] Ti (0iPr) 2 (2.43 mmol) was dissolved in 25 milliliters of hexane in a Schlenck tube. BC13 (5.5 milliliters of a l.OM solution in hexane) was added with a syringe; the color turned orange, and the mixture became cloudy. The mixture was stirred for 3 hours, and then the volatile materials were removed under reduced pressure. The Schlenk tube was sealed and removed from the dry box to a Schlenk line, where it was heated at 70 ° C overnight under a dynamic vacuum, to remove the remaining volatile components. The next day, the Schlenk tube was returned to the dry box, where 0.74 grams of an orange / yellow powder (83 percent) were obtained. The 1 H NMR spectrum of this material indicated that it was [(Me 4 C 5) SiMe 2 NtBu] TiCl 2 compared to the spectrum described in Example 2A.

C. In a dry box, 0.25 grams of [(Me4C5) SiMe2NfcBu] Ti (0LPr) 2 (0.60 millimoles) was dissolved in 20 milliliters of pentane. Et2AlCl (1.2 milliliters of a 1.0 M solution in hexane) was added with a syringe, and the color darkened immediately. The mixture was stirred for 1 hour, and then the volatile materials were removed under reduced pressure to leave an oily yellow solid. The material was formed into a paste in 3 milliliters of pentane, and filtered to leave a bright yellow solid on the filter; this solid was washed with 2 milliliters of additional pentane, and dried under vacuum. The 1 H NMR spectrum of this material indicated that it was extremely pure [(Me 4 C 5) SiMe 2 NtBu] TiCl 2, compared to the spectrum described in Example 2A.

Example 3: Preparation of dimethyl titanium (tertiary butyl amido) dimethyl (tetramethyl-? 5-cyclopentadienyl) silane.

A. In a dry box, 0.26 grams of (Me4C5SiMe2NtBu) Ti (01Pr) 2 (0.63 mMol) in about 15 milliliters of hexane. Trimethyl aluminum (Aldrich, 2M in hexane, 0.95 milliliters, 1.9 millimoles) was added with a syringe. The solution was heated to a slight reflux. After refluxing overnight (approximately 18 hours), the solution became brown. Then the volatile materials were removed under reduced pressure to leave (Me4C5SiMe2NtBu) TiMe2 as a pale chestnut solid. The material was identified by a comparison of its * H NMR spectrum with the spectra of the complex made by other routes. 1 H NMR (C6D6): 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 dry box, 0.255 grams of [(Me4C5) SiMe2NtBu] Ti (0iPr) 2 (0.614 mmol) was dissolved in 20 milliliters of ether. Methyl lithium (1.75 milliliters of a 1.4M solution in ether) was added with a syringe. The mixture was stirred overnight. At the end of this time, the solution was pale brown with a slightly colored precipitate. The volatile materials were removed under reduced pressure to leave a pale solid. The residue was extracted with pentane (20 milliliters), filtered, and dried in vacuo to leave a white crystalline solid. It is 1 H NMR spectrum of this material indicated that it was primarily [(Me4C5) SiMe2NtBu] TiMe2; small peaks of [(Me4C5) SiMe2NtBu] (Me) 0iPr and Li0iPr were also observed.

C. In a dry box, 1.00 grams of [(Me4C5) SiMe2NtBu] Ti (0iPr) 2 (2.41 millimoles) was dissolved in 20 milliliters of hexane. Trimethyl aluminum (3.0 milliliters of a 2.0M solution in hexane) was added with a syringe; the color of the solution darkened slightly. The mixture was heated to a slight reflux with stirring overnight. At the end of this time, the solution became pale brown. The volatile materials were removed under reduced pressure to leave a white crystalline solid (0.79 grams 100 percent). The 1 H NMR spectrum of this material indicated that it was extremely pure [(Me 4 C 5) SiMe 2 NtBu] TiMe 2, by comparison with the spectrum described in Example 3A.

Example 4; Preparation of titanium dibromide (butyl tertiary-amide) d imet i (tetramethyl-5-cyclopentadienyl) silane.

In a dry box, 4.75 grams of SiBr4 (13.7 millimoles;? Ldrich) were weighed into a 100 milliliter flask, and dissolved in 25 milliliters of hexane. [(Me4C5) SiMe2NtBu] Ti (OiPr) 2 (2.25 grams, 6.0 mmol) was added, using 10 milliliters of hexane to wash the material into the flask. The mixture was heated to reflux with stirring for 4 hours; the color changed to a 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 formed into a paste 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 grams of the product (44 percent). The 1 H NMR spectrum of this material indicated that it was [(Me4C5) SiMe2NfcBu] TiBr2 by comparison with the above spectra. XH NMR (C6D6.6): 2.10 (2H), 1.96 (2H), 1.50 (3H), 0.40 (2H).

Claims (24)

1. A process for the preparation of a metal dihydrocarbyloxy coordination complex corresponding to the formula:

cP < MY OR).

wherein: M is titanium, zirconium, or hafnium; Cp * is a cyclopentadienyl group bonded in a? 5 linking mode with M, or a cyclopentadienyl group substituted with from 1 to 4 substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halogen, hydrocarbyloxy, cyano, amino, and mixtures thereof, this substituent having up to 20 non-hydrogen atoms, or optionally, two substituents together cause Cp * to have a fused ring structure; Z is a bivalent moiety comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally sulfur or oxygen, this fraction having up to 50 non-hydrogen atoms, and optionally Cp * and Z together form a cast ring system; Y is a) a bivalent anionic ligand group comprising nitrogen, phosphorus, oxygen, or sulfur, and having up to 20 non-hydrogen atoms, Y being linked with Z and M through said nitrogen, phosphorus, oxygen, or sulfur, and optionally Y and Z together form a fused ring system, or b) a cyclopentadienyl group bonded in a sigma bond with Z mode and in a? 5 linkage mode with M, or a cyclopentadienyl group substituted with 1 to 4 substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halogen, hydrocarbyloxy, cyano, amino, and mixtures thereof, this substituent having up to 20 non-hydrogen atoms, or optionally, two substituents together make And have a cast ring structure; and R, independently in each presentation, is a hydrocarbyl group having from 1 to 20 carbon atoms; comprising the steps of the process: contacting, in the presence of an aprotic organic diluent, a metal compound of the formula: M (0R) 4 wherein M and R are as defined above, with a corresponding dianionic salt compound to the formula: (L + x) y (Cp * -ZY) "2 or ((LX) + x) y (Cp * -ZY)" 2 where: L is a metal of Group 1 or 2 of the Table Periodic of the Elements, X is independently chlorine, bromine, or iodine, x and y are either 1 or 2, and the product of x and y is equal to 2, and Cp *, Z and Y are as defined above; to form the complex of the formula (I). 2. A process according to claim 1, wherein the dihydrocarbyloxy metal coordination complex of the formula (I) corresponds to the formula:

wherein R ', in each presentation, is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halogen, and combinations thereof having up to 20 non-hydrogen atoms, or two R 'groups together form a bivalent derivative thereof; E is silicon or carbon; m is 1 or 2; and M and R are as defined above; and wherein the metal compound of the formula: M (OR) 4 is contacted with a corresponding dianionic salt compound of the formula: (L ++ Xx) \ y (C5Ri'4 _-. (PERD I ' 2) \ m _- »NmR n •)" "2 'or í (Í Í (TLVX) I + t, xÍ I) and (C5R' 4- (ER '2) m- NR') -2 where L, R ', E, X, x, y, and m are as defined above. 3. A process according to claim 1, wherein R, in each presentation, is independently selected from the group consisting of ethyl, isopropyl, normal butyl, and tertiary butyl. 4. A process according to claim 1, wherein the metal compound of the formula: M (0R) 4 is selected from the group consisting of tetra (ethoxy) titanium, tetra (isopropoxy) titanium, tetra (butoxy) normal) titanium. 5. A process according to claim 1, wherein the dianionic salt compound corresponds to the formula: ((MgCl) +) 2 ((Cp * -ZY) "2, or (Li +) 2 (Cp * -ZY ) ~ 2, where Cp *, Z, and Y are as defined above 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 the preparation of a corresponding metal dihydrocarbyl coordination complex to the formula:

Cp * M (II) \ (R,) 2

wherein: M is titanium, zirconium, or hafnium; Cp * is a cyclopentadienyl group bonded in a? 5 linking mode with M, or a cyclopentadienyl group substituted with from 1 to 4 substituents selected from the group consisting of hydrocarbyl, silyl, geryl, halogen, hydrocarbyloxy, cyano, amino , and mixtures thereof, this substituent having up to 20 non-hydrogen atoms, or optionally, two substituents together cause Cp * to have a fused ring structure; Z is a bivalent moiety comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally sulfur or oxygen, this fraction having up to 50 non-hydrogen atoms, and optionally Cp * and Z together form a cast ring system; Y is a) a bivalent anionic ligand group comprising nitrogen, phosphorus, oxygen, or sulfur, and having up to 20 non-hydrogen atoms, Y being linked with Z and M through said nitrogen, phosphorus, oxygen, or sulfur, and optionally Y and Z together form a fused ring system, or b) a cyclopentadienyl group bonded in a sigma bond with Z mode and in a? 5 linkage mode with M, or a cyclopentadienyl group substituted with 1 to 4 substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halogen, hydrocarbyloxy, amino, and mixtures thereof, this substituent having up to 20 non-hydrogen atoms, or optionally, two substituents together cause Y to have a cast ring structure; and R "• independently in each presentation, is a hydrocarbyl group having from 1 to 20 carbon atoms, the process comprising contacting, in the presence of an aprotic organic diluent, a metal coordination complex of the formula:

Cp * M (I)

(0R> 2

wherein R, independently in each presentation, is a hydrocarbyl group having from 1 to 20 carbon atoms, and Cp *, Z, Y, M, are as defined above; with a hydrocarbylating agent comprising a metal or a metal derivative of group 1, 2, 12, or 13, and at least one hydrocarbyl group R "', to form the hydrocarbyl coordination complex of metal of the formula (II) 9. A process according to claim 8, wherein a metal dihydrocarbyl coordination complex corresponding to the formula is prepared:

wherein R ', in each presentation, is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halogen, and combinations thereof having up to 20 non-hydrogen atoms, or two R 'groups together form a bivalent derivative thereof; E is silicon or carbon; m is 1 or 2; and M and R "'are as defined above, by contacting a dihydrocarbyloxy metal coordination complex corresponding to the formula:

wherein: M, R ', E, R, and m are as defined above; with the hydrocarbylation agent. 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, where M and R are as defined above, with a dianionic salt compound corresponding to the formula: (L + x) y (Cp * -ZY) ~ 2 or ((LX) + x ) and (Cp * -ZY) -2 where: L is a metal of Group 1 or 2 of the Periodic Table of the Elements, X is independently chlorine, bromine, or iodine, x and y are either 1 or 2, and the product of x and y is equal to 2, and Cp *, Z, and Y are as defined above;

optionally followed by recovery of the complex corresponding to formula (I). 11. A process according to claim 8, wherein R in each presentation is independently selected from the group consisting of ethyl, isopropyl, normal butyl, and tertiary butyl. 12. A process according to claim 8, wherein R "'is a methyl, benzyl, or neopentyl group 13. A process according to claim 8, wherein the hydrocarbylating agent is selected from the group that consists of R "'Li, R"' 2Mg, RM, MgX ", R" »3A1, and aluminoxanes substituted by R" ', where X "is halogen 14. A process according to claim 13, wherein the hydrocarbylating agent is tri-ethyl aluminum 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. with claim 8, wherein the process is conducted at a temperature between 0 ° C and 100 ° C. 17. A process for the preparation of a metal dihalide coordination complex corresponding to the formula:

Cp * M- (III) (X1)

wherein: M is titanium, zirconium, or hafnium; Cp * is a cyclopentadienyl group bonded in a? 5 linking mode with M, or a cyclopentadienyl group substituted with from 1 to 4 substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halogen, hydrocarbyloxy, cyano, amino, and mixtures thereof, this substituent having up to 20 non-hydrogen atoms, or optionally, two substituents together cause Cp * to have a fused ring structure; Z is a bivalent moiety comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally sulfur or oxygen, having this fraction up to

50 atoms that are not hydrogen, and optionally Cp * and Z together form a fused ring system; Y is a) a bivalent anionic ligand group comprising nitrogen, phosphorus, oxygen, or sulfur, and having up to 20 non-hydrogen atoms, Y being linked with Z and M through said nitrogen, phosphorus, oxygen, or sulfur, and optionally Y and Z together form a fused ring system, or b) a cyclopentadienyl group bonded in a sigma bond with Z mode and in a? 5 linkage mode with M, or a cyclopentadienyl group substituted with 1 to 4 substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halogen, hydrocarbyloxy, amino, - and mixtures thereof, this substituent having up to 20 non-hydrogen atoms, or optionally, two substituents together make Y have a molten ring structure; and X 'independently in each presentation is a halogen group; the process comprising contacting, in the presence of an aprotic organic diluent, a metal coordination complex of the formula:

, Z Cp M (I) (OR)

wherein R independently in each presentation, is a hydrocarbyl group having from 1 to 20 carbon atoms, and Cp *, Z, Y, M, are as defined above; with a halogenating agent comprising at least one member of Group 13 or 14 of the Periodic Table of the Elements, and at least one halogen group X1, to form the metal dihalide coordination complex of the formula (III). 18. A process according to claim 17, wherein a metal dihalide coordination complex corresponding to the formula is prepared:

wherein R ', in each presentation, is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl, germyl, cyano, halogen, and combinations thereof having up to 20 non-hydrogen atoms, or two R 'groups together form a bivalent derivative thereof; E is silicon or carbon; m is 1 or 2; and M and X1 are as defined above; by contacting a metal dihydrocarbyloxy coordination complex corresponding to the formula:

where: M, R1, E, R, and are as defined above; 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), where M and R are as defined above, with a dianionic salt compound corresponding to the formula: (L + x) and (Cp * -ZY) _2 or ((LX) + x) and (Cp * -ZY) -2

where: L is a metal of Group 1 or 2 of the Periodic Table of the Elements, X is independently chlorine, bromine, or iodine, x and y are either 1 or 2, and the product of x and y is equal to 2, and Cp *, Z and Y are as defined above; optionally followed by recovery of the complex corresponding to formula (I). 20. A process according to claim 17, wherein R, in each presentation, is independently selected from the group consisting of ethyl, isopropyl, normal butyl, and tertiary butyl.

21. A process according to claim 17, where X 'is chlorine.

22. A process according to claim 17, wherein the halogenating 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 between 0 ° C and 100 ° C.