MXPA97000816A

MXPA97000816A - Complexes of biciclopentadienil-di

Info

Publication number: MXPA97000816A
Application number: MXPA/A/1997/000816A
Authority: MX
Inventors: D Devore David; K Rosen Robert; J Timmers Francis; C Stevens James
Original assignee: The Dow Chemical Company
Priority date: 1994-08-02
Filing date: 1995-07-14
Publication date: 1998-07-03

Abstract

The present invention relates to a metal complex corresponding to the formula: wherein: M is titanium, zirconium or hafnium in the formal oxidation state of + 2ó + 4; R'y R ", each time they occur, independently selected from hydrogen, hydrocarbyl, silyl, germyl, cyano, halo, and combinations thereof, said R 'and R "having up to 20 non-hydrogen atoms, or adjacent R" adjacent groups and / or "R" groups (when R 'and R "are not hydrogen, halo or cyano) together form a divalent derivative forming a fused ring system, E is silicon, germanium or carbon, x is an integer from 1 to 8; R' '', independently each once it occurs, it is hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, or two R '' 'groups together form a ring system, said R' '' having up to 30 carbon atoms or silicon, and D is a conjugated, stable diene, optionally substituted with one or more groups The hydrocarbyl, silyl groups, hydrocarbylsilyl groups, silylhydrocarbyl groups, or mixtures thereof, said D has from 4 to 40 atoms which are not hydrogen

Description

COMPOUNDS OF BICICLOPENTADIENIL-DIENO This invention relates to certain complexes of transition metals of Group 4 of bicyclopentadienyl having diene ligands and to polymerization catalysts which are obtained therefrom. In one form, this invention relates to complexes of titanium, zirconium or hafnium of bicyclopentadienyl and substituted bis (cyclopentadienyl) having diene ligands in which the metal is in the formal oxidation state of +2 or +4, which is it can be activated to form catalysts for the polymerization of olefins and to methods for preparing said complexes and catalysts. The preparation and characterization of certain zirconium and hafnium complexes of bicyclopentadienyl (Cp2) -diene is described in the following references: Yasuda, et al., Orqanometallics, 1982, 1_, 388 (Yasuda I), Yasuda et al., Acc. Chem Res., 1985, 18. 120 (Yasuda il); Erker, and others, Adv. Orqanomet. Chem., 1984, 2_4, 1 (Erker I); Erker et al., Chem. Ber .. 1994. 127, 805 (Erker II), and US-A-5, 198,401. The last reference describes the use of Cp2Zr (d? Ene) where Zr is the formal oxidation state +4, as an olefin polymerization catalyst in combination with ammonium borate cocatalyst. The transition metal complexes of Group 4 of bicyclopentadienyl in which the metal is in the oxidation state formai +4, and olefin polymerization catalysts formed from said complexes by combination with an agent are known in the art. of activation, for example, alumoxane or ammonium borate. Therefore, U.S. Patent No. 3,242,099 describes the formation of olefin polymerization catalysts by the combination of bicyclopentadienyl metal dihalides with alumoxane. The Patent of E.U.A. No. 5,198,401, discloses transition metal complexes of Group 4 of tetravalent bicyclopentadienyl and olefin polymerization catalysts obtained by converting said complexes into cationic form in combination with an uncoordinated anion. Particularly preferred catalysts are obtained by the combination of ammonium borate salts with the titanium, zirconium or biscyclopentadienyl hafnium complexes. Among the various suitable complexes described are the bis (cyclopentadienyl) zirconium complexes containing a diene ligand attached to the meta! of transition through s-hollows where the transition metal is in its highest formal (+ 4) oxidation state. The present invention provides novel olefin polymerization catalysts, which can be run on a wide range of physical conditions and with a wide range of olefin monomers and combinations of said monomers, thus providing an outstanding opportunity to adapt polyamines having properties specifically desired. The present invention relates to complexes of metals containing two cyclopentadienyl groups or substituted cyclopentadienyl groups, said complex corresponding to the formula: CpCp'MD where: it is titanium, zirconium or hafnium in the formal oxidation state + 2 or +4. Cp and Cp 'are each groups of substituted or substituted cyclopentadienyl being substituted with one to five substituents independently selected from the group consisting of hydrocarbyl, siiyl, germyl, halo, cyano, hydrobiioxy, and mixtures thereof, said substituent having up to 20 atoms that are not hydrogen, or optionally, two of said substituents (except cyano or halo) together, cause Cp or Cp 'to have a fused ring structure, or where a substituent on the Cp and Cp' forms form a portion in loop joining Cp and Cp: D is a stable, conjugated diene, optionally substituted with one or more hydrocarbyl groups, silyl groups, hydrocarbylsilyl groups, siliihydrocarbyl groups, or mixtures thereof, said D having from 4 to 40 non-hydrogen atoms and forming a p-complex with M when M is in the formal oxidation state +2, and forming a s-complex with M, when it is in the oxidation state formai +4. In the diene complexes in which M is in the formal oxidation state +2, the diene is associated with M as a p-complex in which the diene normally assumes a s-trans configuration or a s-cis configuration, in that the length of ligature between M and the four carbons of the conjugated diene, are almost equal (? d as defined below >; -0 15Á) while in complexes in which M is in the formal +4 oxidation state, the diene is associated with the transition metal as an s-complex in which the diene normally assumes a s-cis configuration in that the bond lengths between M and the four carbon atoms of the conjugated diene are significantly different (? d < -0.15Á). The formation of the complex with M in any formal oxidation state +2 or +4, depends on the choice of the diene, the specific metal complex and the reaction conditions used in the preparation of the complex The complexes in which the diene is a -link and M is in the formai +2 oxidation state, constitutes the preferred complexes of the present invention. The present invention also relates to novel methods for preparing the CpCp'D complexes involving the reaction of Group 4 metaie complexes. of bicyclopentadienyl-dihydrocarbyl, -dihydrocarbyloxy, -dihalide or -diamide, wherein the metal is in the formal oxidation state +4 or +3, with a diene, D, and a reducing agent The use of a reducing agent is optional when is started by bicyclopentadiene-dihydrocarbyl complexes More particularly, the metal diene complexes of the present invention can be formed by reacting the following components in any order: 1) a complex of the formula: CpCp'M * X or CpCp'M ** X2 where; Cp and Cp 'are as previously defined; M * is a titanium, zirconium or hafnium in the formal +3 oxidation state; M ** is titanium, zirconium or hafnium in the formal oxidation state +4; and X is a hydrocarbyl group of C-i-e, halide, hydrocarbyloxy of C ?. 6 or C? .6 hydrocarbylamide; 2) a diene corresponding to the formula, D; and 3) optionally when X is C? -6 hydrocarbyl, otherwise, not optionally, a reducing agent. Singularly, when the process is used with diastereomeric mixtures of rae and meso isomers of metallocenes, it can result in the formation of only the diene metal rae complex. Further, in accordance with the present invention, catalysts are provided for polymerization of polymerizable addition monomers, comprising a combination of one or more of the above metal complexes and one or more activation cocatalysts. Preference is given to metal complexes in which the metai is in the +2 formal oxidation state for the formation of the novel catalysts of this invention. Finally, according to the present invention, a polymerization process is provided which comprises contacting one or more polymerizable addition monomers and particularly one or more α-olefins with a catalyst comprising one or more of the above metal complexes and one or more activation catalysts. Generally speaking, the present diene containing complexes are more soluble in hydrocarbon solvents, compared to the corresponding diahalide complexes, and are more stable to reductive elimination and other side reactions than the corresponding hydrocarbon complexes. Diene-containing complex catalyst systems are consequently better accepted for commercial use than alternative systems. All reference to the Periodic Table of ios Elements in the present, should refer to the Periodic Table of the Elements, published and registered by CRCPress, Inc., 1989. Also, any reference to a Group or Groups, should be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system to number groups. The dienes, D, useful, are dienes that do not decompose under reaction conditions used to prepare the complexes of the invention. Under subsequent polymerization conditions or in the formation of catalytic derivatives of the present complexes, the diene group D may be chemically reacted or replaced by another ligand. The complexes of the present invention, wherein M is in the formal oxidation state +2, contains a neutral diene ligand which is coordinated via the formation of the complex by diene double bonds, and not through a form of Resonance of metalacycle containing s-ligatures. The nature of the ligation of the diene to the metal is easily determined by X-ray crystallography or by spectral characterization according to the techniques of Yasuda I, Yasuda II, and Erker I, supra. as the references cited in the present. By the term "-complex", it is understood that both the donation and the subsequent acceptance of electron density by the ligand, are achieved by using p-ligand orbitals, ie, the diene is p-linked (diene p-ligand) ). Witthe scope of the present invention, complexes are also encompassed which contain a diene ligand which is coordinated primarily as s-ligatures containing metallocycle (s-linked diene) wherein the metal is in the formal +4 oxidation state. Said complexes of diene s-ligand to Group 4 metals, have a structure that formally is a metallocyclopentene where the ligation between the metal and the diene (described as structure I) can be described as a 2-butene-1, 4- divalent diyl s-linked to a tetravalent metai, optionally containing only one -linkage involving the p electrons between internal carbons of the conjugated diene. These structures are described as structure ii and structure iii as follows: The nomenclature for said silored diene complexes can be either a metallocyclopentene (referring to the compounds as 2-butene-1,4-diyl) or generically as the mother diene, for example, butadiene. Those of skill in the art will recognize the interchangeability of these names. For example, the biscyclopentadienyl-zirconium complex containing a 2,3-d? Methylene, 3-butadiene-s-linked group, could be termed both bis-cyclopentadienyl-2-butene-2,3-dimethyl-1, 4 -diyl-zircon? oo bis-c? clopentadienyl-2,3-d? met? l-1, 3-butadiene-z? rcon? o. A suitable method for determining the existence of a - or s-complex in conjugated diene containing metal complexes, is the measurement of metal-carbon atomic spaces for the four carbons of the conjugated diene using X-ray crystal analysis techniques. common. Measurements of atomic spaces can be made between the metal and C1, C2, C3 and C4 (M-C1, M-C2, M-C3, M-C4, respectively) (where C1 and C4 are the terminal coals of the group of conjugated diene of 4 carbon and C2 and C3 are the internal carbons of the conjugated diene group of 4 carbons), if the difference between these distances of ligatures,? d, using the following formula: is greater than or equal to -0.15Á, it is considered that the diene forms a p-complex with M and M formally is in the +2 oxidation state. If? D is less than -0.15 Á, it is considered that the diene forms a s-compiejo with M and M is formally in the oxidation state +4. Examples where the above method for the determination of p-complexes has been applied to prior art compounds are found in Erker, et al., Angew. Chem. Int. De. Enq., 1984, 23. 455-456 (Erker iil) and Yamamoto, et al., Organometallics, 1989, 8. 105-119. In the above reference, it was characterized crystallographically (? -alyl) (? 4-butadiene) (? = - cyclopentadienyl) -zirconium. The distances of M-C1 and M-C4 were both 2,360 (= .005j A. The distances of M-C2 and M-C3 were both 2,463 (± .005) A giving a? D of -0.103 Á. reference was shown that the chloride of (? 5-pentamet? lcyclopentadienl) (? "- 1,4-difen? -1,3-butadiene) t? tan? o, has distances of M-C1 and M- C4 of 2.233 (-0.006; TO. The distances of M-C2 and M-C3 were both of 2.293 (± 005)?, Giving a? D of -0.060 Á. Consequently, these two complexes contain ligands of diene-ligand and the metal of each is in the formal +2 oxidation state. Erker i also describes bis (cyclopentadienyl) zirconium (2,3-dimethyl-1,3-butadiene). In this complex, the distances of M-C1 and M-C4 were 2,300 Á. The distances of M-C2 and M-C3 were both of 2.597 Á, giving a? D of -0.297 Á. Consequently, this complex contains a s-ligand diene and the zirconium is in the formal oxidation state. In the use of such X-ray crystal analysis techniques, at least the determination of "good" and preferably "excellent" is used as defined by G. Stout et al., X-ray Structure Determination, A Practical Guide, MacMillan Co., pgs. 430-431 (1968). Alternatively, the complexes in the present invention wherein X is a conjugated diene in the form of a -complex and M is in the formal oxidation state +2, are identified using nuclear magnetic resonance spectroscopy techniques. The teachings of Erker, I to III, supra, C. Krúger, and others. Organometallics. 4, 215-223, (1985), and Yasuda i, supra, describe these well-known techniques for distinguishing between religated complexes and metallocyclic coordination or s-linked diene complexes The teachings of the above references related to p-linked diene complexes and s-linked, is incorporated herein by reference. It should be understood that the complexes of the present can be formed and used as a mixture of the p-complexed and s-acombinated diene compounds wherein the metal centers are in the formal oxidation state +2 or +4. Preferably, the composite in the formal oxidation state +2 is present in a molar amount of 0.1 to 100.0 percent, more preferably in a molar amount of 10 to 100.0 percent, more preferably, in a molar amount of 60 to 100.0 percent. hundred. The techniques of separation and purification of the complex in the formal oxidation state +2 of the above mixtures are known in the art and described for example in the aforementioned references of Yasuda, I, supra, and Erker, I to II! , supra, and, if desired, can be used to prepare the complexes in higher purity. The metal complexes used to form the diene complexes of the present invention are dihaloides, dihydrocarbons, diamides and bis (cyclopentadiene) dialkoxides which have therefore been used in the formation of metallocene complexes, or which have been used in the formation of metallocene complexes. prepare easily using well-known synthetic techniques. An extensive list of biscyliopentadienium complexes is described in US-A-5,198,401. The preferred complexes of the present invention correspond to the formula. wherein M is titanium, zirconium or hafnium, preferably zirconium or hafnium, in the formal oxidation state +2 or +4, R and R "each time they occur, they are independently selected from the group consisting of hydrogen, hydrocarbon, silicon , germyl, cyano, halo and combinations thereof, said R 'and R "having up to 20 non-hydrogen atoms each, or adjacent R' groups and / or adjacent R" groups (when R 'and R "are not hydrogen halo or cyano) together form a bivalent derivative (i.e., a hydrocarbodium syllable group, or germadin) or an R 'and an R "combine together (when the groups of R' and R" are not hydrogen, halo or cyano ) to form a divalent radical (i.e., a hydrocarbyl group, germadiiio or siladiyl) by joining the two substituted cyclopentadienyl groups; and D is a conjugated diene having from 4 to 30 atoms which are not hydrogen, which form a complex with M when M is in the formal oxidation state +2 and an s-complex with M when M is in the formal oxidation state +4. Preferably, R 'and R "independently each time they occur, are selected from the group consisting of hydrogen, methyl, ethyl, and all isomers of propyl, butyl, pentyl and hexyl as well as cyclopentyl, cyclohexyl, norbornyl, benzyl, and trimethylsilyl or adjacent R 'groups or adjacent R "groups on each cyclopentadienyl ring (except hydrogen) are joined thereby forming a fused ring system such as an indenyl group, 2-methyl-4-phenyleidenilium, 2-methyl-4-naphthylidenethio, tetrahydroindenium, fluorenyl, tetrahydrofluorenyl, or octahydrofluorenyl, or an R 'and an R "are united by forming a ligation group 1, 2-ethanole, 2,2-propanediol. or dimethylsilanediyl. Examples of suitable portions of D include? -1-phenyl-1,3-pentadiene; 4-1,4-dibenzyl-1,3-butadiene; 4-2.4-hexadiene; 4-3-methyl-1,3-pentadiene; ? "- 1, 4-d? ToliM, 3-butad? Ene.? -1,4-bis (tr? Meti? L? -1) -1, 3-butadiene, 2,3-d? Met? Lbutad? ene, isoprene, of the foregoing, 1,4-difayne-1,3-butadiene, 1-phenyl-1,3-pentadiene, and 24-hexadiene, ie, 1,3-dienes terminally substituted with di- C 0., 0 hydrocarbyl, generally form p-complexes, while 1,3-dienes internally substituted with Ci.sub.10 hydrocarbyl, such as isoprene or 2,3-dimethylbutadiene, generally form s-compiejos. are 1, 3-butadiene, 2,4-hexadiene, 1-phenyl-1,3-pentadiene, 1,4-diphenylbutadiene or 1,4-ditolylbutadiene terminally substituted with hydrocarbyl of C? -? or- Examples of complexes of the above metals, wherein the metal is titanium, zirconium or hafnium, and preferably zirconium or hafnium include: s-trans (? 4-1, 4-trans, trans-diphenyl-1,3-butadiene) of bis (? 5 -cyclopentadienyl) zirconium, s-cis (2,3-dimethyl-1,3-butadiene) of bis (cyclopentadienyl) zirconium,? -1,4-ditolyl-1,3-butadiene of (bis n3-cyclopentadienyl) -zirconium, 4-1,4-ditolyl-1,3-butadiene of bis (3-cyclopentadienyl) zirconium, 4,4,4-hexadiene of bis (β-cyclopentadienyl) zirconium,? "-3-methyl-1, 3-pentadiene of b? S (= -cyclopentadienyl) zirconium,? 4-1-phenyl-1,3-pentadiene of bis (? 3-cyclopetadienyl) zirconium,? 4-1-phenyl - 1, 3-pentadiene of bis (pentamethyl-? 5-cyclopentadienyl) zirconium,? - 1,4-diphenyl-1-butadiene of bis-pentamethyl-β-cyclopentadieni zirconium,? -1,4-dibenzyl-1,3-butadiene of bis (pentamethyl-? 5-cyclopentadienyl) zirconium,? 4-2,4-hexadiene of bis (pentamethyl-? = - cyclopentadienyl) zirconium,? 4-3-methyl -1, 3-pentadiene of bis (pentamethyl-? 5-cyclopentadienyl) zirconium,? "- 1,4-diphenyl-1,3-butadiene of bis (ethyltetramethyl-? D-cyclopentadienyl) zirconium. -1, 4-dibenzyl-1, 3-butadiene of bis-ethyltetramethyl-β'-cyclopentadienyl) -zirconium, 4-2,4-hexadiene of bis (ethyltetramet? L-? = -cyclopentadienyl) zirconium,? "- 3- methyl-1, 3-pentadiene of b? s (et? ltetramet? l-? 5-c? clopentad? in? l) z? rcon? o, (pentamet? l-? 5-cyclopentadienyl),? 4-1 , 4-d-benzyl-1, 3-butadiene of (? 5-c? Clopentad? In? L) z? Rcon? O, (pentamet? L-? 5-c? Clopentad? In? ),? -2,4-hexadiene of (? Sc? Clopentad? In? L) z? Rcon? O,? 4-1, 4-d? Phen? L-, 3-butadiene of b? S (t-but? L -? 5-c? Clopentad? In? L) -1, 2-z? Rcon? O,? 4-1,4-d? Benc? L-1, 3-butadiene of b? S (t-? but? l-? 5-c? clopentad? in? l) z? rcon? o,? "- 2,4-hexad? ene de b? s (t-but? ltetramet? l-? 5-c? clopentad in? l? -z? rcon? o,? sc? clopentad? in? lo ?,? 4-3-met? l-1, 3-pentad? ene of (tetramethyl-? 3-c? clopentad? in? l) z? rcon? o,? 4-1, 4-d? f in? -1, 3-butadiene of b? s (pentamet? l-? 5-c? clopentad? in? l) z ? rcon? o,? -1-fen? l-1,3-penta diene of b? s (pentamet? l - ?: 5-c? clopentad? in? l) z? rcon? o? 4-3- methyl-1, 3-pentadiene of b? s- (tetramet? l-? 5-c? clopentad? in? l) z? rcon? o,? 4-1,4-d? phen? l-1 , 3-butadiene of b? S (met? L-? 5-c? Clopentad? In? L) z? Rcon? O?,? 4-1,4-d? Benc? L-1 3-butad? b? s ene (? 5-c? clopentad? in? l) z? rcon? o,? 4-2,4-hexadiene b? s (tr? met? ls? l? l?? 5-c "clopentad" in? l) z? rcon? o,? -3-met? l-1, 3-pentad? ene de b? s (tr? met? l? l?? 5-c? clopentad? in? l) -z? rcon? o? "- 1,4-d? phen? l-1,3-buta diene of (? 5-c? clopentad? in? l) (tr? met? ls? l? ? l-? 5-c? clopentad? in? l) z? rcon? o,? 4-1, 4-d? benzyl-1, 3-butadiene of (? sc? clopentad? in? l) (tr? met? l? l?? 5c? clopentad? in? l) z? rcon? o? * - 2,4-hexadiene of (tr? Met? L? L? -? 5-c? Clopentad? In? L) - (pentamet? L-? 5-c? Clopentad? In? L) z? Rcon? O ? "- 3-met? L-1 3-pentad? Ene de b? S (benc? L-? ° -c? Clopentad? In? L) z? Rcon? O,? 4-1, 4-d? f-b-3-butadiene b? s (? d-? nden? l) -z? rcon? o? "- 1 4-d? benc? l-1, 3-butad? ene of b? s (? 5- indenyl) zirconium,? 4-2,4-hexadiene of bis (? s-indenyl) zirconium,? 4-3-methyl-1,3-pentadiene of bis (? 5-indenyl) zirconium,? 4-1-phenyl-1,3-pentadiene of bis (? 5-fluorenyl) zirconium,? 4-2,4-hexadiene of bis? 5-fluorenyl) zirconium, and? 4-3-methyl-1, 3- pentadiene of b? s (? 5-fluorenyl) zirconium. Additional bis-cyclopentadienyl compounds of formula A include those which contain a bridging group that binds the cyclopentadienyl groups. Preferred bridge forming groups and those corresponding to the formula (ER '"2) X where E is carbon, silicone or germanium. R "independently each time it occurs, is hydrogen or a group selected from a ring system, said R '" having up to 30 carbon or silicon atoms, and x is an integer from 1 to 8. Preferably R' "independently each where it occurs, it is methyl, benzyl, tertiary butyl or phenyl Examples of the cyclopentadienyl former bridge former containing complexes, are compounds corresponding to the formula wherein: M, D, E, R '"and x are as previously defined, and R * and R" each time they are presented, are independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R 'and R "having up to 20 non-hydrogen atoms, each, or adjacent R' groups and / or adjacent R" groups (when R 'and R "are not hydrogen, halo or cyano) ) form a divalent derivative (i.e., a hydrocarbaryl, silane, or germadiyl group) by linking the two cyclopentadienyl groups, said bridged structures are especially suitable for the preparation of polymers having a stereoregular molecular structure. the complex is not symmetric or has a steri-directed chiral structure Examples of the first type are compounds having different assembled systems delocalised, such as a cyclopentadienyl group and a fluorenyl group. in Ti (IV) or Zr (IV) were described for the preparation of syndiotactic olefin polymers in Ewen, et al., J. Am. Chem. Soc, 110.6255-6256 (1980). Examples of chiral structures include bis-indenyl complexes. Similar systems based on Ti (IV) or Zr (IV) were described for the preparation of isotactic oiephine polymers in Wild et al., J. Orqanomet. Chem. 232. 233-47, (1982).

The portions bound by illustrative cyclopentadienyl bridges in the complexes of the formula (B) are: s-trans (? 4-1, 4-trans-trans-di-phe nyl-1,3-buta-diene) of dimethyliso-di-diyl-bis ( 2-methyl-4-phenyl) -1-indenyl) zirconium, s-trans (? 4-1,4-trans-trans-diphenyl-1,3-butadiene) of dimethylsilanediyl-bis (2-met? L-4) - (1-naft?!)) - 1 -indenyl) zirconium, s-rans (? -1,4-trans-trans-dip-diphenyl-1,3-butadiene) of 1,2-ethanediyl-bis (2-methyl) -4- (1-phenyl) -1-indenyl) zirconium, s-trans (? 4- 1, 4-trans-trans-d-phenyl-1,3-butadiene) of 1,2-etand ?? lb? s (2-met? l-4- (1-naphthyl) -1-inden? l) zirconium, s-trans (? 4-trans, trans-1,4-d? phen? -1,3-butadiene ) of [1, 2-ethanediylbis (1-indenyl)] z? rcon? o s-trans (? * - trans, trans-1, 4-d if eni I-1,3-butadiene) of [1, 2 ethanediylbs (1-tetrahydroindenyl)] - zirconium, s-trans (? -trans, trans-1,4-diphenyl-1,3-butadiene) of [1,2-ethanedi? lb? s (1- inden? l)] hafn? o, and (trans, trans, -1, 2-diphen? l-1, 3-butad? ene) of [2,2-propaned? l (9-fluoren? l) - (cyclopentaadien? i)] zirconium. In general, the complexes of the present invention can be prepared by combining a diene compound, corresponding to group D in the resulting complex, with a metal complex containing only leaving hydrocarbyl groups. Heating the solution, for example, using toluene in boiling, the reaction can be accelerated. In the case, the metal complex contains hydrocarbyloxy, amide or halogen halides (and otherwise containing the desired structure of the resulting complexes) and optionally when the metal complex contains only leaving hydrocarbyl groups, the metal core, the diene , or the previous mixture of the metal and diene complex, is also in contact with the reducing agent. Preferably, the process is carried out in a suitable non-interfering solvent, at a temperature of -100 ° C to 300 ° C, preferably -78 to 130 ° C, more preferably -10 to 120 ° C. Metal complexes can be used in any formal oxidation state +4 or +3. By the term "reducing agent" as used herein, is meant a metal or compound, which, under reducing conditions, can cause the transition metal to be reduced from the formal oxidation state of +4 or +3 to the formal oxidation state +2. The same procedure is used for the preparation of the diene complexes when M is in the formal oxidation state +2 or in the formal oxidation state +4, the nature of the formal oxidation state of M in the complex, being formed, being determined mainly by the diene employed. Examples of suitable metal reducing agents, are alkali metals, alkaline earth metals, aluminum, zinc and alloys of alkali metals or alkaline earth metals such as sodium / mercury amalgam and sodium / potassium alloy. Specific examples of suitable reducing agent compounds are sodium naphthalenide, potassium graphite, lithium alkyls, aluminum trialkyls and Grignard reagents. The most preferred reducing agents are the alkali metals or alkaline earth metals, C "6-lithium alkyl, C" -aluminum trialkyl and Grignard reagents. especially lithium, n-butyl lithium and triethylaluminum. Especially preferred is the use of a Ci_6-lithium or triethylaluminum alkyl reducing agent. The highly preferred diene compounds are 1,3-pentadiene; 1,4-diphenyl-1,3-butadiene; 1-phenyl-1,3-pentadiene; 1,4-dibenzyl-1,3-butadiene; 2,4-hexadiene; 3-methyl-1,3-pentadiene, 1,4-dithioii-1,3-butadiene; and 1,4-bis- (trimethylsiiii) -1,3-butadiene. All geometric isomers of the above compounds can be used. The reaction medium suitable for the formation of the complexes are aliphatic and aromatic hydrocarbons and halohydrocarbons, ethers, and cyclic ethers. Examples include straight or branched chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methicyclohexane, methylcycloheptane, and mixtures thereof; hydrocarbyl substituted aromatic and aromatic compounds such as benzene, toluene, xylene, dialkyl ethers of C1.4, dialkyl ether derivatives of C? -4 of (poly) alkylene glycols and tetrahydrofuran. Mixtures of the above list of suitable solvents are also suitable. The recovery process involves separation of the resulting byproducts and devolatilization of the reaction medium. If desired, extraction in a secondary solvent may also be employed. Alternatively, if the desired product is an insoluble precipitate, filtration or other separation technique may be employed. The present inventors have further discovered that the metal complexes of Group 4 of bis-cyclopentadienyl ansa-rae (where "rae" refers to a racemic mixture of enantiomers), form only stable complexes with the conjugated diene, particularly with a 1, Trans-3-butadiene, trans-terminally disubstituted. The meso-bisciciopentadienium diene complexes of corresponding Group 4 metals are less stable and non-recoverable, unless extreme care is taken. Accordingly, this discovery allows the skilled person to separate mixtures of diastereomers of biscyclopentadienyl-Group 4 metals complexes, which contain hydrocarbyl, hydrocarbyloxy, halide or amide leaving groups, only by contacting the mixture with a conjugated diene of C4- or, and the reducing agent, where required, and recovering the ansa-rae bis-cyclopentadienyl diene complex, Group 4 metal. In a further embodiment, the complex containing the corresponding halide, can be regenerated in the highly bissacpentadienyl ansa-rae form. by contacting the diene-ansa-rac bis-cyclopentadienyl diene complex with a halogenating agent, such as hydrochloric acid or BCl 3. Said process is highly convenient in order to form catalyst components that preferentially form isokácic polymers of prochiral olefins, such as propylene.

In greater detail, the above process comprises combining in a solvent in any order: 1) a mixture of rae- and meso-diastereomers of a compound having the formula: wherein: M is titanium, zirconium or hafnium; X is halogen, C? .6 hydrocarbyl, C? .6 hydrocarbyloxy, or C? -6 dihydrocarbylamide, E, R "'and x are as previously defined, and R' and R" each time they occur, They are selected independently from! group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano. Halo and its combinations, said R "and R" having up to 20 hydrogen atoms or each, or adjacent R 'groups and / or adjacent R "groups (when R' and R" are not hydrogen, halo or cyano) together form a bivalent derivative (i.e., a hydrocarbyaliyl, sil ai or germadiyl group) linking two of the cyclopentadienyl groups, 2) a conjugated diene of C4-0, D, and 3) optionally when X is hydrocarbyl of C? .6, not optionally in some way, a reducing people, and recovering the rac-diasteromer from the formula: Preferred starting complexes are diastereomer mixtures of b? S (? Nden? L) meta? Ocenes, corresponding to the formula meso b? S (? Nden? L) rae b? S (? Nden? L) metallocene metallocene or hydrogenated derivatives thereof, wherein, M, X, E, x, and R '"are as previously defined , and R each time it is presented, is independently selected from the group consisting of hydrocarbyl hydrogen, silyl, germyl and combinations thereof, said R, having up to 20 non-hydrogen atoms, each or adjacent R groups in each indenyl system separated, they together form a divalent derivative (ie, hydrocarbaryl, siladiyl or germadiyl group) thereby forming an additional fused ring Examples of suitable precursor compounds are found in W. Spaleck, et al., Organomet., 13, 954-963 ( 1994) The complexes become catalytically active by combining with one or more activating cocatalysts, using an activation technique, or a combination thereof Activating cocatalysts suitable for use herein include alumoxanes oligomer cos, especially methylalumoxane, methylalumoxane modified by trnsobutylaluminum, or ditsobutylalumoxane; Strong Lewis acids (the term "strong Lewis acid" as used herein) is defined as Group 13 compounds substituted by trihydrocarbon, especially tr (hydrocarbyl) aluminum compounds or tr? (hydrocarbon) boron and halogenated derivatives thereof, having from 1 to 10 carbons in each halogenated hydrocarbon or hydrocarbon group, more especially, the perfluorinated tri (aryl) boron compounds, and even more especially tris (pentaphenyl ( borane); amine, phosphine, aliphatic alcohol, and mercaptan adducts of tri (C? -? 0 hydrocarbyl) halogenated boron compounds, especially such adducts of perfluorinated tri (aryl) boron compounds; non-polymeric, ionic activation compounds , compatible, non-coordinating, (including the use of said compounds under oxidation conditions), bulk electrolysis (explained in more detail below), and combinations and techniques of the previous activating cocatalysts. Iivation and activation techniques above, have been previously taught with respect to different metal complexes in the following references: EP-A-277,003, US-A-5,153,157, US-A-5,064,802, EP-A-468,651, EP-A -520,732, and WO 93/03250. Combinations of strong Lewis acids, especially the combination of a trialkyl aluminum compound having from 1 to 4 carbons in each alkyl group and a tri (hydrocarbyl) boron compound having from 1 to 10 carbons in each hydrocarbon group, especially tris (pentafiuorophenyl) borane; further combinations of said mixtures of strong Lewis acid with a polymeric or oligomeric alumoxane; and combinations of a single strong Lewis acid, especially tris (pentafiuorophenyl) borane with a polymeric or oligomeric alumoxane, are especially suitable activating cocatalysts.

When such strong Lewis acid cocatalysts are used to polymerize higher α-olefins, especially propylene to form homopolymers thereof, it has been found especially desirable to also contact the catalyst / cocatalyst mixture with a small amount of ethylene or hydrogen ( preferably at least one mole of ethylene or hydrogen per mole of metal complex, suitable from 1 to 100,000 moles of ethylene or hydrogen per mole of metai complex). This contact can occur before, after or simultaneously, by contacting the superior α-olefin. if the Lewis acid activated catalyst compositions above or are treated in the following manner, there are both extremely long induction periods and no polymerization. The ethylene or hydrogen can be used in a suitably small amount so that no significant effect on the properties of polymers is observed. For example, polypropylene having physical properties equal to or greater than polypropylene prepared by the use of other metallocene catalyst systems, is prepared in accordance with the present invention. Therefore, the invention further comprises an activated polymerization catalyst system, comprising in combination: a) a metal complex corresponding to the formula: CpCp'MD wherein: M, Cp, Cp ', and D are as previously defined, b) a Lewis acid, and c) ethylene or hydrogen, the amount of ethylene or hydrogen, being at least equal to the amount necessary to activate the catalyst system for polymerization of an α-olefin of C3 or higher, preferably , at least 1 mole per mole of metal complex, more preferably from 1 to 100,000 mole per mole of metal complex. The volume electrolysis technique involves the electrochemical oxidation of the metal complex under electrolysis conditions in the presence of a supporting electrolyte comprising an inert non-coordinating anion. In the art, the supporting electrolyte solvents and electrolytic potentials for electrolysis are used in such a way that the electrolysis byproducts which could return to the complex of catalytically inactive metals, are not formed substantially during the reaction. More particularly, suitable solvents are materials that are liquid under the conditions of electrolysis (generally temperatures of 0 to 100 ° C), capable of dissolving the supporting electrolyte, and inert "Inert solvents" are those that are not reduced or oxidized under the reaction conditions employed by electrolysis. It is generally possible in view of the desired electrolysis reaction to choose a solvent and a supporting electrolyte which is not affected by the electrical potential used for the desired electrolysis. Preferred solvents include difluorobenzene (ortho, meta, or para isomers), dimethoxyethane, and mixtures thereof. The electrolysis can be carried out in a normal electrolytic cell, containing an anode and cathode (also referred to as the working electrode and electrode respectively). Suitable materials for cell construction are glass, plastic, ceramics and glass-coated metal. The electrodes are prepared from inert conductive materials, by which conductive materials are understood that are not affected by the reaction mixture or reaction conditions. Platinum or palladium are preferred inert conductive materials. Normally, an ion-permeable membrane such as a fine glass frit separates the cell into separate compartments, the working electrode compartment and counter-electrode compartment. The working electrode is immersed in a reaction medium comprising the complex of metals to be activated, solvent, support electrolyte, and any other materials desired to moderate electrolysis or stabilize the resulting complex The electrode is immersed in a mixture of the solvent and supporting electrolyte. The desired voltage can be determined by theoretical calculations or by experimentally sweeping the cell using a reference electrode such as a silver electrode submerged in the cell electrolyte. The current of the booster cell is also determined., the current extracted in the absence of the desired electrolysis. The electrolysis is completed when the current falls from the desired level to the level of reinforcement. In this way, the complete conversion of the initial metal complex can be easily detected. Suitable supporting electrolytes are salts comprising a cation and an inert anion, compatible non-coordinating, A ". Preferred support electrolytes are salts corresponding to the formula: G + A" wherein: G + is a cation which does not react with the starting complex and resulting; and A "is a non-coordinating, compatible anion Examples of cations, G +, include ammonium or phosphonium cations substituted by tetrahydrocarbon having up to 40 non-hydrogen atoms.A preferred cation is the tetra-n-butylammonium cation During the activation of the compounds of the present invention by mass electrolysis, the cation of the supporting electrolyte passes to the counter electrode and A "migrates to the working electrode to become the anion of the resulting oxidized product. Either the solvent or the cation of the supporting electrolyte is reduced in the counter electrode in the same molar quantity with the amount of the oxidized metal complex formed in the working electrode. Preferred support electrolytes are tetrahydrocarbylammonium salts of tetrakis (perfluoroaryl) borates having 1 to 10 carbons in each hydrocarbyl group, especially tetra-n-butylammonium tetrakis (pentafluorophenyl) borate. Suitable compounds useful as a cocatalyst in an embodiment of the present invention comprise a cation which is a Bronsted acid capable of donating a proton and a non-coordinating, compatible, inert anion A. The preferred anions are those containing only one Coordination complex comprising a metal having charge or a metalloid matrix whose anion is capable of balancing the charge of the active catalyst species (the metal cation) which is formed when the components are combined. to be displaced by olefinic, diolefinic and acetylenically unsaturated compounds, or other neutral Lewis bases such as ethers or nitriles Suitable metals include, but are not limited to, aluminum, gold and piatine Suitable metalloids include, but are not limited to boron, phosphorus, and silicon Compounds containing anions that comprise complex coordination complexes All of a single metal or metalloid atom are, of course, well known, and many, particularly such compounds containing a single boron atom in the anionic portion, are commercially available. Therefore, said compounds of a single boron atom are preferred. Preferably, said cocatalysts can be represented by the following general formula: (L * -H) + d (Ad ") wherein: L * is a neutral Lewis base; (L * -H)" is a Bronsted acid; Ad "is a compatible, non-coordinating anion, which has a charge of d-, and d is an integer from 1 to 3. More preferably Ad" corresponds to the formula: (M'k + Qn) d-where: k is an integer from 1 to 3; n is an integer from 2 to 6; n-k = d; M 'is a selected element of Group 13 of the Periodic Tabia of the elements; and Q independently each time it occurs, it is selected from hydride, dialkylamido, halide, alkoxide, aryloxide, hydrocarbon, and hydrocarbyl radicals, the said Q having up to coals as long as no more than one Q presentation is halide. In a more preferred embodiment, d is one, ie the counterion has a single negative side and corresponds to the formula A-The activating cocatalysts comprise boron, which are particularly useful for the preparation of catalysts of this invention, can be represented by the following general formula (L * -H) + (BQ \) where: L * is as previously defined, B is boron in a valence state of 3; and Q 'is a fluorinated hydrocarbyl group of C1.20. More preferably, Q 'each time it is presented, is a fluorinated aryl group, especially a pentafluorophenyl group. Illustrative but not limiting examples of boron compounds that can be used as an activating cocatalyst in the preparation of the improved catalysts of this invention are trisubstituted ammonium salts such as trimethylammonium tetraphenyl borate, triethylammonium tetraphenyl borate, tripropylammonium tetraphenyl borate, tri (n-butyl) ammonium tetraphenyl borate, tri (t-butyl) ammonium tetraphenyl borate, N, N-dimethylanilinium tetraphenyl borate, N, N-diethianiumium tetraphenyl borate, N, N-dimethyl-tetrapheni-borate (2,4 , 6-trimethyianylium), tetrakis (pentafluorophenyl) borate of tmethyl ammonium, tetrakis (pentaf luorofenyl) borate of triethylammonium, tet rachis (pentafluorophenyl) borate of tppropylammonium, tetrakis (pentafiuorofenii) borate of tri (n-but? I) ammonium, tet rachis (pentafluorophenyl) borate of tri (sec-butyl) ammonium, tetraquís (pentafluorofen? l) borate of N, Nd? met? lani? n? o, tet raquis (pentafluorofen? l) bo N, N -dietilanilinio, tet raquis (pentafluorofenii) bo r N, N-dimethyi- (2,4,6-tpmethylanilinium), trimethylammonium tetrakis- (2,3,4,6-tetrafluorophenolborate, triethylammonium tetrakis- (2,3,4,6-tetrafluorophenyl) borate), tetra- (2,3,4,6-tetrafluorophenyl) borate of tripropylammonium, tetrakis- (2,3,4,6-tetraflurophenyl) borate of tri (n-butyl) ammonium, tetrakis- (2,3,4,6 -tetrafluorophenyl) dimethyl (t-butyl) ammonium borate, tetra- (2,3,4,6-tetrafiuorophenyl) borate of N, N-dimethylanilinium, tetrakis- (2,3,4,6-tetrafluorophenyl) borate of N , N-diethylanilinium, and N, N-dimethyl- (2,3,4,6-trimethylanilinium) tetrakis- (2,3,4,6-fluorophenyl) borate; dialkyl ammonium salts, such as di- (i-propyl) ammonium tetrakis (pentafluorophenyl) borate, and dicyclohexylammonium tetrakis (pentafluorophenyl) borate; and trisubstituted phosphonium salts, such as triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (a-tolyl) phosphonium tetrakis (pentafluorophenyl) borate, and tri (2,6-dimethyphenic!) phosphonium tetrakis (pentafluorophenyl) borate. The preferred cations of [L * -H] + are N, N-dimethylanilinium and tributylammonium. Another ion-forming activating cocatalyst comprises a salt of a cationic oxidizing agent and a non-coordinating compatible anion represented by the formula. wherein: Oxe + is a cationic oxidizing agent that has a charge of e +; e is an integer from 1 to 3; and A d- ", and d are as previously defined Examples of cationic oxidizing agents include, ferrocenium, hydrocarbyl substituted ferrocenium, Ag +, or Pb + 2. Preferred embodiments of Ad" are those anions previously defined with respect to the acid of Bronsted containing activation cocatalysts, especially tetrakis (pentafluorophenyl) borate. Another ion-forming activating catalyst comprises a compound which is a salt of a carbenium ion and a compatible, non-coordinating anion represented by the formula: <+ A "where: © + is a carbenium ion of C? -2o; and A "is as previously defined. A preferred carbenium is the tritium cation, which is triphenylcarbenium. An additional suitable ion-forming activating cocatalyst comprises a compound which is a silicon ion salt and a non-coordinating, compatible anion represented by the formula: ################################################################################# is a C1.20 hydrocarbyl, s is 0 or 1, X # is a neutral Lewis base, and A "is as previously defined Preferred silylium salt activating cocatalystsare triethyl silicate tetrakispentafluorophenylborate of triemethyl lysine tetrakispentafluorophenylborate and ether-substituted adducts thereof. Silylium salts have previously been described generically in J. Chem. Soc. Chem. Comm., 1993, 383-384, as well as Lambert, J.B., et al., Organometallics, 1994, 13, 2430-2443. The above activation technique and the ion-forming catalysts are also preferably used in combination with a tri (hydrocarbyl) aluminum compound having from 1 to 4 carbons in each hydrocarbyl group, an oligomeric or polymeric aiumoxane compound, or a mixture of a tp (hydrocarbyl) aluminum compound having from 1 to 4 carbons in each hydrocarbyl group and a polymeric or oligomeric aiumoxane. The molar ratio of the catalyst / cocatalyst employed varied preferably from 1: 10,000 to 100: 1, more preferably from 1: 5000 to 10: 1, more preferably from 1: 1000 to 1: 1. In a particularly preferred embodiment of the invention, the cocatalyst can be used in combination with an aluminum trihydrocarbyl compound of C3.30 or oligomeric or polymeric alumoxane. Mixtures of activating cocatalysts can also be used. These aluminum compounds can be used for their beneficial ability to sweep impurities such as oxygen, water, and aldehydes from the polymerization mixture. Preferred aluminum compounds include C2.6 tpalkylaluminum compounds, especially those wherein the alkyl groups are ethyl, propyl, isopropyl, n-butyl. isobutium, pentiium, neopenil, or isopentium and methylalumoxane modified methylalumoxane and diisobutylalumoxane. The molar ratio of the aluminum compound to metal complex is preferably from 1: 10,000 to 1000: 1; more preferably from 1: 5000 to 100: 1, more preferably, from 1: 100 to 100: 1. The combination of the CpCp'D complexes with strong Lewis acid activating cocatalysts, in a preferred embodiment, corresponds to one of the two ionic zwitterionic equilibrium structures, of the formula: wherein: M is titanium, zirconium or hafnium in the formal oxidation state + 4; Cp and Cp 'are each a substituted or unsubstituted cyclopentadienyl group bonded in a ligation mode? = To M, said substituted cyclopentadienyl group being substituted with : C D I-T \ CR3 CR5R6 (C) \ * ^ \ CR? R2 CR4 (BQ3) CR5R6 CR4 (BQ,) '\ CpCp' M + ./:CR3 (D) CR? R2 from one to five substituents independently selected from the group consisting of hydrocarbyl, silium, germium, halo, cyano, and mixtures thereof, said substituent having up to 20 atoms without hydrogen, or optionally two of said substituents other than cyano or halo together, cause Cp or Cp 'to have a fused ring structure, or a substituent on Cp and Cp' forms a binding portion that binds Cp and Cp '; Q, independently whenever it is present, is selected from hydride, dialkylamido, halide, haloxide, aryioxide, hydrocarbyl, and halo-substituted hydrocarbon radicals, said Q having up to 20 carbon atoms with the proviso that in more than one presentation, Q is halide; Ri, R2, R3, R4, R5, R6 are independently hydrogen, hydrocarbyl, silyl, and combinations thereof, each of said Ri to R6 having up to 20 non-hydrogen atoms and B is boron in a valence state of 3. Preferred equilibrium zwitterionic structures correspond to the formula: wherein: R1, R2, R5 and ß are hydrogen; R3 and R4 are hydrogen, C? -4 alkyl or phenyl. M is zirconium in the formal oxidation state +4, and R 'and R "each time they occur, are independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R 'and R "having up to 20 atoms that are not hydrogen each, or adjacent R' groups and / or adjacent R groups (when R 'and R" are not hydrogen, halo or cyano) together form a divalent derivative (i.e. , a hydrocarbyl, siladiyl, or germadiyl group that forms a fused ring system) combine to form a divalent radical (ie, a hydrocarbyldiyl, germadiyl or siladiyl group) by linking the two cyclopentadienium groups. balance are more highly preferred, corresponding to the formula: R where.

M is zirconium in the formal oxidation state +4; Ri, R2, Rs and Re are hydrogen; R3 and R4 are hydrogen or methyl; and R 'and R "each time they occur, are independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R' and R" each having up to 20 atoms that they are not hydrogen, or the adjacent R 'groups and / or adjacent "R" groups (wherein R 'and R "are not hydrogen, halo or cyano) together form a divalent derivative (i.e., a hydrocarbony, siiadiyl, or germadiyl group, which forms a fused ring system) or an R' and an R" together (when the R 'and R "groups are not hydrogen, halo or cyano), they combine to form a divalent radical (i.e., a hydrocarbon, germadiiio or siiadiio group) by linking the two cyclopentadieniio groups. to optimize ethylenically and / or acetylenically unsaturated monomers having from 2 to 20 carbon atoms either alone or in combination Preferred monomers include the C2.10 α-olefins especially ethylene, propylene, isobutylene, 1-butene, 1- hexene, 4-methylene-1-pentene, and 1-octene and mixtures thereof Other preferred monomers include vinylcyclohexene, vinylcyclohexane, styrene, styrene substituted with C? -4 alquilo alkyl, tetrafluoroethylene, vinylbenzocyclobutane, ethylidene norbornene, and piping. , 4-hexad? Eno.

When the bridged cyclopentadienyl polymerization catalysts present are used to polimepzar prochiral olefins, syndiotactic or isotactic polymers can be obtained. How I know. used herein, the term "syndiotactic" refers to polymers having a stereoregular structure of more than 50 percent, preferably greater than 75 percent syndiotactic of a racemic triad as determined by nuclear magnetic resonance spectroscopy of | 3C. Inversely, the term "isotactic" refers to polymers having a stereoregular structure greater than 50 percent, preferably greater than 75 percent isotactic of a meso triad as determined by 13C nuclear magnetic resonance spectroscopy. Said polymers can be usefully employed in the preparation of articles and articles having an extremely high resistance to deformation due to the effects of temperature via compression molding, moideo by injection or other suitable technique. The ethylene / 1-olefin copolymers of the present invention are the characteristic of the type of ethylene polymers that can be obtained with metallocene catalysts. The polyolefins that can be produced with the catalysts of the present invention, vary from elastomeric to plastomeric, that is, products that are substantially non-elastomeric, depending on the monomers. amounts of monomers and polymerization conditions used. As used herein, the term "elastomepco" means polymers having values of tensile modulus as measured by ASTM D-638 of less than 15,000 N / cm2, preferably less than 5000 N / cm2, and more preferably less than 500 N / cm2 These products find application in all the uses developed before for said polyolefins and can be manufactured in said end-use products by means of the method developed below for polyolefins including, for example, molding, casting, extrusion and rotation. Polyolefins obtained with the catalysts of the present invention are useful in such end-use applications as packaging films, including shrink wrapping applications, foams, coatings, insulating devices, including for wire and cable, and household articles. the polyolefins made with the catalysts of the present invention, have superior properties in these applications on the materials used herein in these applications using the tests that have been established to measure the end-use performance intended by tests not applied herein, to measure performance in said end-use applications. In general, polymerization can be achieved at conditions well known in the prior art for polymerization reactions of the Ziegier-Natta or Kaminsky-Sinn type ie temperatures of 0-250 ° C and pressures of atmospheric pressure to 3000 atmospheres. If desired, suspension, slurry solution, gaseous phase or high pressure may be used, either batch or continuous or under other process conditions, including the recycling of condensed monomers or solvent. Examples of such processes are well known in the art, for example, WO 88/02009-A1 or US-A-No. No. 5,084,534, describes conditions that can be employed with the polymerization catalysts of the present invention. A support can be used, especially silica, alumina or a polymer (especially polytetrafluoroethylene or a polyolefin), and is conveniently used when catalysts are used in a gas phase polymerization process. Such supported catalysts are generally not affected by the presence of hydrocarbons. aliphatic or aromatic liquids, in such a way, that they may be present in the presence of liquid aliphatic or aromatic hydrocarbons in such a way that they may be present under the use of condensation techniques in a gas phase polymerization process. Methods for the preparation of supported catalysts are described in numerous references, examples of which are US-A-Nos. 4,808,561, 4,912,075. 5,008,228, 4,914,253, and 5,086,025, and are suitable for the preparation of supported catalysts of the present invention. In most polymerization reactions, the molar ratio of catalysts: polymerizable compounds employed is from 1 O "12: 1 to 10'1: 1, more preferably from 10" 12: 1 to 1 O "5: 1. The solvents suitable for solution processes, suspension, slurry or polymerization at high pressures, are non-coordinating inert liquids. Examples include straight and branched chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof, cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; perfluorinated hydrocarbons such as perfluorinated C-? 0 alkanes, and alkyl-substituted aromatic and aromatic compounds such as benzene, toluene, and xylene. Suitable solvents also include liquid olealines which can act as monomers or comonomers including ethylene, propylene, butadiene, cyclopentene, 1-hexene, 3-methyl-1-pentene, 1,4-hexadiene, 1-octene, 1-decene, styrene , divinylbenzene, allylbenzene, and vinyltoluene (including all isomers alone or mixed). Mixtures of the above are also suitable. The catalysts can also be used in combination with at least one additional homogeneous or heterogeneous polymerization catalyst, in separate reactors connected in series or in parallel to prepare mixtures of polymers having suitable properties. Examples of said processes are described in WO 94/00500 and WO 94/17112. Having described the invention, the following examples are provided as an additional illustration and should not be construed as limiting. Unless stated otherwise, all parts and percentages are expressed on a weight basis. Example 1: Preparation of bis (trans) 4- (4-1, 4-trans, diphenyl-1,3-butadiene) (? 5-cyclopentadienyl) zirconium. In a glovebox under inert atmosphere, 586 mg (2.01 mmol) of (C5H5) 2ZrCI2 and 413 mg (2.00 mmoies) of trans, trans-1,4-diphenyl-1,3-butadiene are combined in 90 ml of mixed alkanes (isopar E '", available from Exxon Chemicals Inc.) To the desired slurry, 1.60 ml of 2.5 M n-butyl lithium is added. Immediately the mixture turns dark red, after stirring at 25 ° C during 2 hours, the mixture is refluxed for 3 hours. The hot solution is filtered. The red solid residue is extracted with a total volume of 90 ml of hot toluene. The extracts were filtered and combined with the hexanes filtrate. The total volume of the solution was concentrated at 40 ml under reduced pressure. At this point, a red precipitate formed. The mixture was heated until the solid was redissolved and the solution was placed in a freezer (-25 ° C).

The dark red crystals were subsequently collected in a glass frit. Drying under reduced pressure gives 210 mg (25 percent yield) of (? 4-1, 4-trans, trans-diphenyl-1,3-butadiene) of (CsH5) 2Zr as verified by the 1H NMR analysis . The product has a cis-trans configuration of 95 percent, and s-cis of 5 percent. Example 2: Preparation of s-cis (2,3-dimet? I-1,3-butad? Ene) of bis (? 5-cyclopentadienyl) zirconium.

In a glove box under inert atmosphere, 586 mg (2.01 mmol) of (C5H5) 2 ZrCI2 and 2.5 ml (22 mmol) of 2,3-dimethyl-1,3-butadiene were combined in 90 ml of mixed alkanes. To the stirred slurry, 1.60 ml of 2.5 M n-butyl lithium was added. The color slowly changed to red. After stirring for 1 hr at 25 ° C, the mixture was refluxed for 34 hr. The hot solution was then filtered using a Celite ™ brand diatomaceous earth filter aid from Fisher Scientific Ind. The filtrate was concentrated to 50 ml and the deep red filtrate was placed in the freezer (-25 ° C). Dark crystals were collected by filtration, and dried under reduced pressure to give 234 mg (39 percent yield) of (2,3-dimetii-1,3-butadiene) of (CsHs) 2Zr as verified by NMR analysis 'H. The product had a s-cis configuration for the diene. Example 3: Combination of Lewis acid with s-trans (β "- 1, 4-trans, trans-diphenyl-1,3-butadiene) of bis (c? Clopentadienyl) z? Rcon? O In a glovebox in an inert atmosphere, 8.4 mg (0020 mmoles) of s-trans (? "- 1, 4-trans, trans, diphenyl-1,3-butadiene) of (CsH5) 2Zr of Preparation # 1 and 10.0 mg (0.020 mmoles) of B (C6F5) 3 are combined in .75 ml of benzene-d6 to form a homogeneous solution. The NMR analysis' shows the reagents that are going to be completely consumed. Example 4 Combination of Lewis acid with s-c? S (2,3-dimethyl-1,3-butadiene) of b? S (cyclopentadienyl) z? Rcon? O.

In a glovebox under inert atmosphere, 5.9 mg (0.0195 mmol) of (2,3-dimethyl-1,3-dimethyl-1,3-butadiene) of (C5H5) 2Zr and 10.0 mg (0.0195 mmol) of B ( C6F5) 3 were combined in 0.75 ml of benzene-d6 to give a homogeneous solution. 1 H NMR analysis indicated that the mixture has been clearly converted to the zwitterionic compound (CH2CMe = CMeCH2B (C6F5) 3) of (C5Hs) 2Zr 'or its equivalent isomer? 3. (C6D6), 5.31 (s, 5H), 4.91 (s, 5H), 2.37 (d, 10.5 Hz, 1H), 1.09 (s, 3H), 0.93 (d, 10.5 Hz), -0.3 (broad) and -0.7 ppm (broad). Example 5 Polymerization using a combination of s-trans (? 4-1, 4-trans, trans-diphenyl-1,3-butadiene) of (CsHs) 2Zr and B (C6F6) 3. A two-liter reactor is charged with 746 g of mixed alkanes and 120 g of 1-octene comonomer. Hydrogen was added as a molecular weight control agent by differential pressure expansion of a 75 ml addition tank from 2.1 MPa to 1.9 MPa. The reactor was heated to the polymerization temperature of 140 ° C and saturated with ethylene at 3.4 MPa. 5 00 μmol of the catalyst combination of Example 3 (0.00500 M solutions in toluene) were transferred to a catalyst addition tank. Polymerization was initiated by injecting this solution into the reactor contents. The polymerization conditions were maintained for 10 minutes with ethylene provided on demand at 3.4 MPa. The polymer solution was removed from the reactor and combined with 100 mg of a hidden phenol antioxidant (Irganox ™ 1010 available from Ciba Geigy Corp.). The volatiles were removed from the polymer in a vacuum oven set at 120 ° C for about 20 hours. The polymer yield is 16.8g. Example 6: Preparation of Ethylene / Propylene copolymer using (2, 3-dimethyl-1,3-butadiene) of [bis (cyclopentadienyl)] zirconium and B (C6F5) 3. A two liter reactor was charged with 656 g of mixed alkanes and 207 g of propylene comonomer. Hydrogen was added by differential pressure expansion of an additional 75 ml tank from 2.1 MPa to 1.9 MPa. The reactor was heated to the polymerization temperature of 140 ° C and saturated with ethylene at 3.4 MPa. 10 μmol of (2,3-dimethyl-1,3-butadiene) of [bis (cyclopentadienii)] zirconium and 10 μmoies of B (C6F5) 3 in toluene were transferred to a catalyst addition tank. Polymerization was initiated by injecting this solution into the reactor contents. The polymerization conditions were maintained for 20 minutes with ethylene provided on demand at 3.4 MPa. The reaction mixture was removed from the reactor and the volatiles were removed in a vacuum oven set at 120 ° C for about 20 hours, 21.0 g of an ethylene / propylene copolymer were obtained. Example 7: Combination of s-trans (? - 1, 4-trans, trans-diphenyl-1, 3-butadiene) of (C5H5) 2Zr with tetraqu? S (pentafluorophen? L) dimethylaluminum borate.

In a glove box under inert atmosphere, 0.043 g (0.010 mmol) of s-trans (4-1,4-trans, trans-diphenyl-1,3-butadiene) of bis-cyclopentadienyl-zirconium were dissolved in 20 ml. of toluene followed by the addition of 0.0780 g (0.099 mmol) of dimethylanilinium tetrakis (pentafluorophenyl) borate using 10 ml of toluene to wash the solids in the reaction flask. After one hour, the solvent was removed under reduced pressure. The product was washed with pentane (3x10 ml with drying after the final wash). The product was isolated as an oil. Example 8: Electrolytic preparation of [tetrakis (pentafluorophenyl) borate] of s-trans (? 4-1,4-trans, trans-diphenyl-1,3-butadiene) of (C5Hs Zr.) A normal H cell for electrolysis comprising two electrode wells separated by a thin glass frit, platinum mesh work and counter electrodes, and a silver reference electrode, are placed inside an inert atmosphere glove box filled with argon.Each half of the cell is filled with solvent of 1,2-difluorobenzene (5 ml in the working compartment, 4 ml in the opposite compartment) and tetrakis (pentafluorophenyl) borate of tetra-n-butylammonium supporting the electrolyte (8 mmoles) The complex, s-trans (? "-1, 4-trans, trans-d? Phenyl-1, 3-butadiene) of b? S (c? Clopentadienyl) Zr (0.017 g) is placed in the working compartment. of the working electrode to determine the voltage to be applied during electrolysis.The solution is agitated and the potential rises to the first oxidation wave of the complex and adjusted to obtain a current of 1.5 mA. The applied potential is turned off when the current falls to 30 percent of its original value having passed a total of 3.3 coulombs. This represents a conversion of 72 percent. The solution of the working compartment is then pipetted into a round bottom flask and the solvent is removed under vacuum. The resulting solid product is extracted with toluene (2.0 ml) and transferred directly to the polymerization reaction in Example 9. Example 9: Polymerization using the catalyst of Example 8. A stirred 2 liter reactor was charged with the desired amounts of mixed alkane solvent and 15 g of a 1-octene comonomer. Hydrogen was added as a molecular weight control agent by differential pressure expansion (200? KPa) of an addition tank of about 75 ml at 2.1 MPa. The reactor was heated to the polymerization temperature and saturated with ethylene at 3.4 MPa. 5.00 μmol of the catalyst of Example 8 were dissolved in toluene and transferred to a catalyst addition tank and injected into the reactor. The polymerization was allowed to proceed for the desired time with ethylene provided on demand at 3.4 MPa. After 15 minutes of operation time, the solution was removed from the reactor and quenched with isopropanol. An occult phenol antioxidant was added to the polymer solution. The resulting solid polymer of ethene and 1-octene was dried in a vacuum oven set at 120 ° C for about 20 hours. Example 10: Polymerization using s-trans (? 4-1, 4-trans, trans-diphenyl-1,3-butadiene) of (CsHs) 2Zr with alumoxane. A stirred 5 L autoclave reactor was charged with 1850 g of anhydrous hexane through a mass flow meter. A solution containing 100 μmol of triisopropylaluminum-modified methylalumoxane (MMAO), obtained from Akzo Corporation) in 10 ml of hexane, was then added to the reactor via a pressurized stainless steel cylinder before heating to 80 ° C. At this point, the reactor pressure was increased to 70 kPa by the addition of hydrogen followed by enough ethylene to bring the total pressure to 1.21 MPa. The ethylene was continuously supplied to the reactor by means of a demand on-line power regulator. 12.5 μmol of the diene complex of Example 1, was letred in hexane and then added to the reactor to initiate the polymerization. After 30 minutes, the ethylene flow was stopped and the reactor was vented and cooled. The resulting polyethylene was filtered and dried at 80 ° C overnight in a vacuum oven. Example 11: Preparation of s-trans - (? 4-1, 4-trans, trans-diphenyl-1,3-butadiene) of rac- [1,2-ethanediylbis (1-indenyl)] zirconium. In a glove box under inert atmosphere, 837 mg (2.00 mmol) of rac - [(1, 2-ethaned?? L? B? S (1-inden? L)] zirconium and 413 mg (2.00 mmol) were combined. mmoles) of trans, trans-1,4-d-phenol-1, 3-butadiene, in approximately 90 ml of mixed alkanes To this mixture, 1.60 ml of 2.5 M butyl lithium in mixed alkanes (4.00 mmoles) were added. This mixture immediately turned dark red.After stirring at room temperature for half an hour, the mixture was heated to reflux for two and a half hours.The solution was cooled and filtered through Celite brand filtration aid. The solid residue was extracted using a total of 100 ml of toluene The extracts were filtered and the filtrates were combined The filtrate was concentrated at 20 ml under reduced pressure and the concentrate was cooled to 30 ° C. A red solid was added. It was collected in a glass frit.The volatiles were removed from the solid under reduced pressure to give 767 mg of a solid red talin The identity and purity of the compound was confirmed using 1H NMR spectroscopy. (C6D6), 7.55 (d, 8.8 Hz, 2H), 7.2 (m), 7.3-6.8 (m, 4H). 6 76 (m.2H), 6.60 (d, 8.5 Hz, 2H), 5.23 (d, 3.3 Hz, 2H), 4.58 (d, 3.3 Hz, 2H), 3.35 (m, 2H), 3.01 (m, 4H) ) and 1.83 ppm (m, 2H). Example 12: Combination of Lewis acid with s-trans (α -1, 4-trans, trans-diphenyl-1,3-butadiene) of rac- [1,2-etand nlb? S (1-indenyl)] zirconium . In a glovebox under inert atmosphere, 9 mg (approx 0.2 mmoles) of s-trans (α "- 1, 4-trans, trans-diphenyl-1,3-butadiene) of rac - [bis-1 2 -etandi? lb? s (1-indenyl)] z? rconium and 10 mg of (0 02 mmol) of B (C6F5) 3 was combined with 0.75 ml of benzene-d6 to give a homogeneous solution of the complex as established by 1 H NMR analysis The dissolved reaction product is useful as a polymerization catalyst for the polymerization of ethylene following the procedure of Example 10. Example 13: Preparation of s-cis (2,3-dimethyl-1,3-butadiene ) of bis (n-butylcyclopentadienyl) zirconium In a glove box in an inert atmosphere, 2.01 mmoles of (n-butylC5H4) 2ZrCl2 and 22 mmoles of 2,3-dimethyl-1,3-butadiene were combined in 90 ml. of hexane To the stirred slurry was added 1.60 ml of n-butyl lithium 2.5 M. Color changed slowly to red After stirring for 1 hr at room temperature, the mixture was heated to reflux for 3 hours. it was then filtered using a diatomaceous earth filter aid. The filtrate was concentrated to 50 ml and the deep red filtrate was placed in the freezer (-25 ° C). The dark crystals were collected by filtration and dried under reduced pressure to give s-cys (2,3-dimet? L-1, 3-butadiene) of (n-but¡¡H4) Zr based on 1 H NMR analysis . Example 14: Combination of Lewis acid with s-cis (2,3-dimethyl-1,3-butadiene) of bis (n-butylcyclopentadienyl) zirconium. In a box of gloves in an inert atmosphere, 0.0195 mmoles (2,3-dimethyl-1,3-butadiene) from (n-butii C5H4) 2Zr and 0.0195 mmoies of B (C6F5) 3 were combined in 0.75 ml of benzene-d6 to give a homogeneous solution. The conversion to (n-butyl C5H4) 2Zr + (CH2CMe = CMeCH2B (C6F5) 3- or its? Equivalent isomer) was stabilized by H-NMR analysis. The resulting product is useful as a catalyst for the polymerization of ethylene as described in Example 10. Example 15: Preparation of rac (trans, trans-1,4-diphenyl-1,3-butadiene) [1,2 -etandiylbis (1- (2-methyl-4-phenyl) indenyl) zircon? o. In a box of gloves in an inert atmosphere, they were combined 106. 6 ml (0.170 mmoles) of rac- [1,2-ethanediylbis (1- (2-methyl-4-phenyl) indenyl)] zirconium dichloride and 35.1 ml (0.170 mmoles) of trans, -1,4-diphenyl- 1,3-butadiene were combined in approximately 50 ml of toluene. To this mixture was added 0.14 ml of 2.5 M butyl lithium in mixed aléanos (0.35 mmoles). After quenching at about 25 ° C for two hours, the mixture changed from yellow to orange. The mixture was heated in toluene (approximately 80 ° C) for three hours, during which time it became dark red. The solution was cooled and filtered through a Celite ™ brand filter aid. The volatiles were removed from the solid under reduced pressure to give a red solid. This was dissolved in 15 ml of mixed alkanes which was then removed under reduced pressure. 1 H NMR spectroscopy showed the desired p-diene product as well as some butylated material. The solid residue was dissolved in toluene and heated to reflux for five hours. The volatiles were then removed under reduced pressure and the residue was dissociated in a small amount of mixed aiicans (ca.10 ml) the resulting solution was cooled to -30 ° C. A solid was isolated by decanting the solid solution and removing the remaining volatiles from the solid under reduced pressure. 1 H NMR spectroscopy showed the desired compound, (trans, trans-1,4-di-phenyl n-1,3-buta-diene) of rac- [1,2-ethanediibis (1- (2-methyl-4-phenyl) ) indenyl)] zirconium as the main component containing an indenyl type lingado. Example 16: Preparation of terpolymers of Ethylene / Propylene / Diene A batch reactor of 2 I was charged with 500 ml of mixed alkanes, 75 ml of 5-ethylidene-1-norbornene, and 500 ml of liquefied propylene. The reactor was heated to 60 ° C, and saturated with ethylene at 3.4 MPa. In a dry box in an inert atmosphere, 10 μmoles of a 0.005 M solution in toluene of (trans, trans-1,4-diphenyl-1,3-butadiene of rac- [1,2-ethanediylbis (1- (2)] were combined. -methyl-4-phenyl) indenyl)] zirconium and 10 μmol of a 0.005 m solution of B (C6F5) 3 and the mixture was transferred to the reactor to initiate the polymerization.After 15 minutes, the reactor is vented and the solution The polymer solution was combined with the 100 mg of antioxidant and the volatiles were removed under reduced pressure in order to isolate the ethylene / propylene / ethylidene norbornene elastic terpolymer. Example 17: Preparation of Ethylene / Propylene / 7-methyl-1,6-octadiene copolymer. The procedure of Example 16 was substantially followed, except that 75 ml of 7-methyl-1,6-octadiene was used in place of the ethylidene norbornene. After removing the solvent, an elastic ethylene / propylene / 7-methyl-1,6-octadiene terpolymer was obtained. Example 18: Preparation of Copolymer from Ethylene / Pro Pilen / Pipe Rile The procedure of Example 16 was substantially followed, except that 75 ml of piperylene (1,3-pentadiene) was used in place of the ethylidene norbornene. After removing the solvent, an ethylene / propylene / piperylene elastomeric terpolymer was obtained. Example 19. Preparation of Isotactic Polypropylene. A two-liter reactor was charged with 500 ml of mixed alkanes, and 500 ml of liquefied propylene. Ethylene (10 μmol) was added to the reactor. The reactor was heated to 60 ° C, and 10 μmol of the combination of s-trans (4-1,4-trans-trans-diphenyl-1,3-butadiene) of rac-1, 2- [bis- (1-inden? L) ethanod? Il] z? Rconium with B (C6F5) 3 of Example 12 (0.005 M toluene solution) was added slowly in order to control the exothermic polymerization. After 15 minutes of polymerization at 60 ° C, the reactor was vented and the contents of the reactor were stirred. The solvent was removed under vacuum and the crystalline polypropylene, isotactic solid, was isolated. Example 20. Preparation of (2,3-dimethyl-1-3-butadiene) 2-propanod? Il (c? Clopentadienyl-9-fluoren? L) z? Rconium In a glovebox under inert atmosphere, 5 g of 2,2-propanediol dichloride (c? ciopentad? in? l-9-fluoren? l) z? rcon? o (11.56 mmoies) and 0.95 g of (2,3-dimetii-1, 3-butad ? ene) (11.56 mmoles) (available from Boulder Scientific Inc.) were combined in 500 ml of toluene. This mixture was stirred and 9.3 ml of 2.5 M n-butyl lithium was added. After stirring for 2 hours at room temperature, the mixture was filtered through a frit funnel. Toluene was added to the frit funnel and solids were removed. The total volume of the filtrate was concentrated under reduced pressure to obtain the product in crude form. The crude product can be purified by recrystallization in order to obtain a product of higher purity. Example 21: Preparation of syndiotactic polypropylene. A two-liter reactor was charged with 500 ml of mixed alkanes, and 500 ml of liquefied propylene. A small amount of ethylene (0.001 weight percent based on propylene) was added to the reactor. The reactor was heated to 60 ° C. In a dry box in an inert atmosphere, 10 μmoles of 2,2-propanediyl (cyclopentadienyl-9-fluorenyl) z? Rconium (2,3-dimetii-1,3-butadiene) were combined. , with 10 μmoies of B (C6F5) 3 (toluene solution 0.005 M). The mixture was added slowly to the reactor in order to control the exothermic polymerization. After 15 minutes of polymerization at 60 ° C, the reactor was vented and the contents of the reactor were stirred. The solvent was removed under vacuum and crystalline solid syndiotactic polypropylene was isolated. Example 22 Preparation of syndiotactic polypropylene. Substantially the procedure of Example 21 was followed, except that ethylene was not added to the reactor and the catalyst mixture is 10 μmoles of 2,2 (2,3-d? Met? L-1,3-butadiene) of 2.2 - propanediyl (cyclopentadienyl-9-fluorenyl) zirconium (solution in toluene 0.005 M) combined with 10 mmoies of metiiaiuminoxane (MAO) (solution in toluene 1.0 M). The mixture was slowly added to the reactor in order to control the exothermic polymerization. After 15 minutes of polymerization at 60 ° C, the reactor was vented and the contents of the reactor were removed. The solvent was removed under reduced pressure and crystalline syndiotactic polypropylene, solid, was isolated. Example 23: Preparation of Supported Catalysts (a) Preparation of Support Dry silica (2.5 g, Davison 948, dried at 800 ° C) was lettered with 10 ml of 1.0 M methyalianuminoxane (MAO) 1.0 M in toluene) and the mixture was stirred for 30 minutes. The die was filtered and washed five times with 10 ml portions of pentane. The washed slurry was dried under vacuum. (b) Preparation of supported s-trans (? 4-1, 4-trans-trans-diphenyl-1,3-butadiene) bis (n-butylcyclopentadienyl) zirconium catalyst was prepared analogously to s-trans (? 4-1 , 4-trans-diphenyl-1,3-butadiene) of bis (cyclopentadienol) zirconium (Example 1). A 100 ml flask was charged with 0.50 g of s-trans (4-1,4-trans-trans-diphenyl-1,3-butadiene) of b ?s (n-butylcyclopentadyl) -zirconium (1.17 mmol) ). A solution of MAO (50 ml of a 1.0 M toluene solution) was added. The solution was stirred for five minutes followed by the addition of 2.5 g of the treated silica obtained from part (a) above. The mixture was stirred for five minutes, and the toluene was removed under vacuum to give the supported catalyst. Example 24: Polymerization of slurry using supported catalyst. A 1 liter reactor was charged with 400 ml of hexane and 0.2 ml of triethylaluminum (1.6 M in heptane). The reactor was heated to 80 ° C and ethylene was provided on demand at 0.7 MPa. After, the reactor was saturated with ethylene, 0.5 g of the prepared supported catalyst obtained from step (b) above was added to start the polymerization. After 60 minutes, the reaction was stopped by venting the reactor and the solid polyethylene was recovered. Example 25: Preparation of s-trans- (? -1,4-trans-trans-diphenyl-1,3-butadiene) of rac-dimethylsilyl-bis (2-methyl-4- (1-naphthyl) -1 ~ indenil) zirconium. In a glove box under inert atmosphere, 5.0 g of rac-dimethylsilyl-bis (2-methyl-4- (1-naphthyl) -1-indenyl) dichloride (6.84 mmoy) dichloride and 1,408 g of trans, trans-1,4-diphenyl-1,3-butadiene (6.84 mmol) were combined in 500 ml of toluene. This mixture was stirred and 5.5 ml of n-butyl lithium 2.5M was added. After stirring for 2 hours at room temperature, the mixture was heated to reflux for 3 hours. The hot solution was filtered through a frit funnel. Hot toluene was added to the frit funnel and the solids were extracted. The total volume of the filtrate was concentrated under reduced pressure to obtain the product in crude form. The crude product can be purified by recrystallization in order to obtain a product of higher purity. Example 26: Polymerization using supported catalyst. Silica was dried (2.5 g, Davison ™ 952, available from Davison Catalyst Corp.) at 600 ° C. To this dry silica was added 25 ml of toluene in a dry box in an inert atmosphere. The slurry was stirred while 0.50 g of (? 4-1, 4-trans-trans-diphenyl-1,3-buta-diene) of rac-dimethylsilyl-bis (2-methyl-4-naphthi-1-) was added. indenii) zirconium. After 10 minutes, the solvent was removed under reduced pressure to give a supported catalyst. A reactor of 21 was charged with 500 ml of mixed alkanes and 500 ml of liquefied propylene, and 5 ml of 1M methylaluminoxane (MAO) in toluene was added. The reactor was heated to 60 ° C. 0.50 g of silica supported catalyst was added to the reactor to initiate the polymerization. After 30 minutes, the reactor was vented and the high melting crystalline polypropylene was recovered. A 2-I reactor was charged with 500 ml of mixed alkanes, 500 ml of mixed alkanes, 500 ml of liquefied propylene, and 0.2 ml of triethylaluminum (1.6 M in heptane) were added. The reactor was heated to 60 ° C. A small amount of ethylene (0001 weight percent based on propylene) was added to the reactor. In a dry box under inert atmosphere, 10 μmoles of (? "- 1, 4-trans-trans-d? Phen? T-1, 3-butadiene) of bis (2-met? I-4-naft? I-1-inden? L) z? Rcon? O (0 005 M in toiuene) were combined with 10 μmoies of B (C6F5) 3 (solution 0.005 M in toluene.) This mixture was added slowly to the reactor in order to control the exothermic polymerization.After 15 minutes of polymerization at 60 ° C, the reactor was vented and the contents of the reactor were stirred. vacuum and crystalline solid isotactic polypropylene was isolated Example 28: N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate activation cocatalyst polymerization Substantially the procedure of Example 27 was repeated except that 10 μmol of a 0.005 M toluene solution of N, N-Dimethylaminoium tetrakis (pentafluorophenyl) borate was used in place of cocatalyst of B (C6F5) 3. After 15 minutes of polymerization at 60 ° C, the reactor was vented and the contents of the reactor were stirred. The solvent was removed under vacuum and the crystalline solid isotactic polypropylene was isolated. Example 29: Polymerization at high pressure. A 100 ml stirred steel autoclave was used, equipped to perform Ziegler polymerizations at pressures up to 250 MPa and temperatures up to 300 ° C. The reaction system was equipped with a thermocouple and a pressure transducer to continuously measure the temperature and pressure, and with means to supply, purified ethylene, nitrogen, hydrogen, and 1-butene. The reactor was also equipped with means to continuously introduce a measured fiow of catalyst solution and equipment to rapidly ventilate and extinguish the reaction and to collect the polymer product. The catalyst was prepared by combining 564 mg of s-transír-l, 4-trans-trans-diphenyl-1, 3-butadiene) of bis (n-butyl-cyclopentadienyl) zirconium with 1.0 I of MAO 0.8M in 10 l of toluene in a dry box under inert atmosphere. This catalyst solution is continuously fed into the reactor at a rate necessary to maintain a temperature of 180 ° C in the reactor. During the operation, ethylene and 1-hexene are pressurized in the reactor at a total pressure of 100 MPa at a mass flow of 50 kg / hr. The reactor is stirred at 1000 rpm. A solid copoiimer of ethylene and 1-hexene is obtained. Example 30: High Pressure Polymerization The procedure of Example 29 was repeated, except that MAO was not used and the catalyst was prepared simultaneously by adding equimolar amounts of 0.005 M solutions of s-trans (? -1,4-trans-trans-diphenyl-1,3-butadiene) of bis (n-butylcyclopentadienyl) zirconium and B (C6FS) 3 to the flow stream of 1-hexene just before the reactor. A solid copoiimer of ethylene and 1-hexene was obtained. Example 31: Preparation of s-trans (? 4-trans, trans-1,4-diphenyl-1,3-butadiene) of rac- [1,2-ethanediylbis (1-indenyl)] zirconium from a dichloride mixture of rae and meso [1,2-ethanediylbis (1-inden? l)] zirconium. In a glovebox under inert atmosphere, 418.5 mg (1.00 mmol) of 1,2-ethanediylbis (1-indenyl) dichloride] z? Rcon? O (95 percent rae, 5 percent meso by NMR analysis' H) and 207 mg (1.00 mmoies) of trans, trans-1, 4-d if eni i-1,3-butadiene were combined in approximately .70 ml of mixed alkanes. To this mixture was added 0.80 ml of 2.5 M butyl lithium in mixed alkanes (2.00 mmol). This mixture immediately turned dark red. After stirring at about 25 ° C for half an hour, the mixture was heated to reflux for three hours. The solution was cooled and filtered through a Celite ™ brand filter aid and mixed alkane filtrate was placed aside. The solid residue was extracted twice with 30 ml of toluene, the extracts were filtered and the filtrates were combined. The filtrate was concentrated at 150 ml under reduced pressure and the concentrate was cooled to -30 ° C. A red solid was collected in a glass frit. The volatiles were removed from the solid under reduced pressure to give 200 mg of a red crystalline solid. The identity and purity of the compound was confirmed using 1 H NMR spectroscopy and found not to contain any mesoesomer. The toluene filtrate was combined with the filtrate of mixed aganes and the volatiles were removed under reduced pressure. The solid was briefly washed with pentane at -30 ° C. Drying under reduced pressure gave a red powder. 1H-NMR analysis showed that the product was (trans, trans-1,4-dif eni I-1,3-butadiene) of rac- [1,2-etandiiibis (1-indenii)] zirconium contaminated with some diene free but not with meso product. Example 32: Preparation of rac- [1,2-ethanedi-lb? S (l-indenyl)] zircon (trans, trans-1, -difenyl-1,3-butadiene) of rac - [1,2-ethanodiiibis (1-indenii) jzirconium and HCi.

A concentrated solution of (trans, trans-1,4-diphenyl-1,3-butadiene) of rac-1, 2-ethanediylbis (1-ydenyl)] zrconium was prepared in C6D6 and the 1H NMR spectrum obtained . To this deep red solution was added 0.1 ml of 12M aqueous HCl. The mixture turned bright yellow rapidly, and yellow microcrystals formed on the walls of the sample tube. 1 H NMR analysis showed that the rac- [1,2-ethanediylbis (1-inden? L)] zirconium dichloride sample had no meso isomer present. The solvent was decanted from the yellow crystals which were then washed with 0.75 ml of CDCI3 which was also decanted from the remaining solid. C6D6 was added to the solid and the H-NMR spectrum was obtained. The spectrum showed that the material was rac- [1,2-ethanedi-lb? S (1-yen'i)] zirconium dichloride with the most of the missing organic fragments. Example 33: Preparation of (trans, trans-1, -d? F-enyl-1,3-butadiene) rac- [1,2-ethanediylbis (1-tetrahydroinden? L)] z? Rcon? O In a Glove box under inert atmosphere, 213 mg (0.500 mmol) of rac- [1,2-ethanedi-lb? s (1-tetrahydroindenyl)] zirconium dichloride and 103 mg (0.500 mmol) of trans, trans-1, 4-d? Phenyl-1, 3-butadiene was combined in approximately 35 ml of mixed aces. To this mixture were added 0.40 ml of 2.5 M butyl lithium in mixed alkanes (1.0 mmol). This mixture gradually turned dark red. After stirring at about 25 ° C for half an hour, the mixture was heated to reflux for half an hour. The solution was cooled through Celite ™ brand filter aid. The residue was washed three times each with 10 ml of mixed alkanes. The solid residue was extracted with toluene (five times with 12 ml each), the extracts were filtered and the filtrates were combined. The volatiles were removed from the filtrate under reduced pressure to give 98.0 mg of a red crystalline solid. The identity and purity of the compound was confirmed using * H NMR spectroscopy. (C6D6), 7.50 (d, 7.7 Hz, 4H), 7.29 (m, 4H), 7.02 (t, 7.4 Hz, 1H), 4.70 (d, 3 Hz, 2H), 4.26 (d, 3 Hz, 2H ), 3.57 (m, 2H), 3.15 (m, 2H), 2.8 (m, 2H), 2.5 (m), 2.0 (m), 1.8 (m) and 1.4 ppm (m). Example 34: Preparation of (trans, trans-1,4-diphen-l, 3-butadiene) of rac- [1,2-ethanediylbis (1-indenyl)] hafnium. In a glovebox under inert atmosphere, 505.7 mg (1.00 mmol) of rac- [1,2-ethanediylbis (1-indenyl)] hafnium dichloride and 260.3 mg (1.00 mmoi) of trans, trans-1, 4- dif-enyl-1,3-butadiene were combined in approximately 70 ml of mixed alkanes. To this mixture 0.80 ml of butyl iiiium 2.5 M in mixed alkanes (2.0 mmoles) was added. This mixture gradually became dark orange. After stirring at about 25 ° C for five hours, the mixture was filtered through Celite'M brand filter aid and the filtrate concentrated under reduced pressure to an orange powder. The H-NMR analysis in C6D6 showed that the solid is a mixture of dibutyl hafnium complex and free diene. The solid was dissolved in 50 ml of toluene and heated to reflux for two hours, during which time the solution turned dark red. The volatiles were removed under reduced pressure. The solid residue was washed with mixed alkanes. The solid was dried under reduced pressure to give 217 mg of a red powder. The product was identified using 1 H NMR spectroscopy,? (C6D6), 7.50 (d, 9.6 Hz, 2H), 7.28 (m), 7.19, 6.98 (m), 6.74 (m), 6.60 (d, 8.5 Hz), 5.17 (d, 3 Hz, 2H), 4.68 (d, 3 Hz, 2H), 3.36 (m, 2H), 2.96 (m) and 1.70 ppm (m, 2H). Example 35: Preparation of (trans, trans-1,4-dif-enyl-1,3-buta-diene) of [2,2-propanediyl (1-fluorenyl) (cyclopentadienyl)] zirconium.

In a glovebox under inert atmosphere, 433 mg (1.00 mmol) of [2,2-propanediyl (1-fluorenyl) (c? Clopentadien? L)] zirconium dichloride (previously recrystallized from boiling toluene) and 206 mg ( 1.00 mmoies) of trans. trans-1,4-d-phenyl-1,3-butadiene, were combined in approximately 60 ml of toluene. To this mixture was added 0.80 ml of 2.5 M butyl lithium in mixed alkanes (2.0 mmoles). This mixture immediately turned dark red. After stirring at room temperature for an hour and a half, the mixture is filtered through Celitel brand filter aid? "The filtrate was concentrated at 15 ml under reduced pressure and cooled to 30 ° C. A dark purple crystalline solid was collected in a glass frit and the probe it was washed once with cold-blended aicans to give 226 mg of solid.The identity and purity of the compound was confirmed using 1 H NMR (C6D6), 7.4 (d), 7.25 (m), 7.0 (m), 6.85 spectroscopy. (m), 6.6 (d), 6.55 (m), 5.6 (s), 5.1 (s), 4.3 (m), 1.6 (s) and 1.2 ppm (m) Examples 36-39 of the Polymerization Procedure in Solution All solvents and liquid monomers were sprayed with nitrogen and, together with any spent gases, were passed through activated alumina before use, a two liter reactor was charged with mixed alkane solvent and optionally 1-octene or styrene comonomer Propylene monomer, if used, was measured using a MicroMotion ™ brand gas flow rate meter that gives the monomer Total number supplied, if desired, hydrogen is added by differential pressure expansion of a 75 ml addition tank of 2070 kPa at a lower pressure. usually 1890 KPa. The batch quantities of ethylene are then added using the flow meter. If the ethylene monomer is used as required, the contents of the reactor are first heated to within 5 ° C of the polymerization temperature and saturated with ethylene normally at 3450 kPa. The catalyst and cocatacator is combined in toluene and transferred to a catalyst addition tank. When the reactor content is at the desired operating temperature, the polymerization is initiated by injecting the catalyst solution into the reactor contents. The polymerization temperature is maintained by external resistive heating and internal cooling during the desired operating time. The pressure is maintained at 3450 KPa if the demand is provided on request. Occasionally, additional catalyst and cocatalyst solution is added to the contents of the reactor in the above manner. After the desired operating time has passed, the contents of the reactor are removed and combined with an occult phenoxy antioxidant solution. The polymer is isolated by removing the volatile components of the reaction mixture in a vacuum oven set at 120 to 130 ° C for about 20 hours. Example 36 Preparation of isotactic polypropylene using (trans, trans-1,4-dif-enyl-1,3-butadiene) of rac- [1,2-ethanodiiib? S (1-indenyl) zirconium and B (C6F5) 3. The general procedure was followed using 719 g of mixed alkanes, hydrogen at 170 KPa, 200 g of propylene monomer with a temperature of 70 ° C and a polymerization time of 60 minutes. The catalyst was prepared by combining 2 [mu] mls of (trans, trans-1,4-d? Phen? -1,3-butadiene) of rac - [(1,2-ethano? Lb? S (1-inden? l)] z? rconium and 2 μmoles of BíCeFs in toluene The yield of isotactic polypropylene was 181.5 g, (74 percent m pentadiene by 13 C NMR analysis) Example 37. Preparation of isotactic polypropylene using (trans, trans-1,4-d? phen? l-1,3-butadiene) of rac- [1,2-ethano? lb? s (1-indenyl)] z? rcon? oy B (C6F5) 3 with The polymerization conditions of Example 36 were repeated substantially except that initially a small amount of ethylene was added to the reactor content instead of hydrogen, the amounts of ingredients used being 723 g of solvent, 3 g of ethylene, 200 g of propylene monomer with a polymerization temperature of 70 ° C and an operation time of 30 minutes. The catalyst was prepared by combining 2 [mu] mmol of (trans, trans-1,4-dif-en-1-1, 3-butadiene) of rac- [1,2-ethanediylbis (1-indenyl)] zirconium and 2 [mu] mol of B ( C6F6) 3 in toluene. 94.2 g of isotactic polypropylene / ethylene copolymer was obtained (73 percent m.pentad. By 13 C NMR analysis). Example 38: Preparation of isotactic polypropylene using (trans, trans-1,4-diphenyl-1,3-butadiene) of rac- [1,2-ethanediylbis (1-indenyl)] zirconium and tetrakis (pentafluorophenyl) borate of N, N-dimethyl Minium, [Me2NHPh] + [B (C6F5)]: The general procedure was followed using 715 g of mixed aiolis, hydrogen at 170 KPa, 200 g of propylene monomer, a polymerization temperature of 70 ° C and a polymerization time of 67 minutes. The catalyst was prepared by combining 4 μmol of (trans, trans-1,4-dif-enyl-1,3-butadiene) of rac- [1,2-ethanediylbis (1-indenyl)] zirconium and 4 μmol of [Me2NHPh] + [B (C6F5)] in toluene. 164.8 g of crystalline polypropylene were obtained. Example 39. Preparation of Polymerization of Ethylene / Propylene Copolymer using (trans, trans-1,4-dif-en-i-1-3-butadiene) of rac- [1,2-ethanediylbis (1-tetrahydro? Nden? L)] zirconia and B (C6F5) 4.

The general procedure was followed using 840 g of mixed aiicans, hydrogen at 220 kPa, 75 g of propylene monomer and ethylene monomer on demand at 3450 KPa with a polymerization temperature of 130 ° C and a polymerization time of 15 minutes. The catalyst was prepared by combining 3 μmoies of (trans, trans-1,4-diphenyl-1,3-buta-diene) of rac- [1,2-ethanediylbis (1-indenii)] zirconium and 3 μmol of B (C6F5) 4 in toiueno. 19.6 g of crystalline ethylene / propylene copolymer were obtained. Example 40. Preparation of isotactic propylene using (trans, trans-1,4-dif-enyl-1,3-butadiene) of rac-1, 2-ethanedi-ils (1-2-metii-4-phenyl) indenii )] zirconium and B (C6F5) 4 with hydrogen. The general procedure was followed (except as noted below) using 723 g of solvent, hydrogen at 690 kPa. 201 g of propylene monomer with a polymerization temperature of 70 ° C and a polymerization time of 30 minutes The catalyst was prepared by combining 2 μmol of (trans, trans-1,4-d? Phen? M, 3-butadiene) of rac- [1,2-ethanediylb? s (1- (2-met? l-4-phen? l)? nden? l)] z? rconium and 2 pmol of B (C6F5) 4 in toluene. The valve at the bottom of the reactor was capped and the contents of the reactor could not be emptied immediately after the polymerization. The reactor was vented The reactor was then re-supplied with nitrogen gas at 2 8 MPa and vented. This was repeated twice more to remove the unreacted propylene monomer. The contents of the reactor were then rapidly heated to 160 ° C and the contents were stirred as a solution. 107 2 g of isotactic polypropylene was obtained (57 percent m pentad by analysis of RMC 13C). Example 41. Preparation of Polymerization of Ethylene / Propylene Copoiimer using (trans, trans-1,4-dif in il-1,3-butadiene) of [2,2-propanediyl (9-fluorenyl) (cyclopentadienyl)] zirconium and B (C6F5) 3. The general procedure was followed using 719 g of mixed alkanes, hydrogen at 170 kPa, 200 g of propylene monomer and 26 g of ethylene monomer with a polymerization temperature of 70 ° C and a polymerization time of 30 minutes. The catalyst was prepared by combining 10 μmol of (trans, trans-1,4-diphenyl-1,3-butadiene) of [2,2-propanediyl (1-fluorenyl) (cyclopentadienyl)] zirconium and 10 μmol of B (C6F5) ) 3 in toluene. 69.4 g of amorphous ethylene / propylene copolymer were obtained. Example 42. Preparation of Syndiotactic Propylen using (trans, trans-1,4-diphenyl en-1,3-butadiene) of [2,2-propanediyl (1-fluorenyl) (cyclopentadienyl)] zirconium and methylalumoxane (MAO). The general procedure was followed using 719 g of mixed alkanes, hydrogen at 170 kPa, 200 g of propylene monomer and 26 g of ethylene monomer with a polymerization temperature of 70 ° C and an operation time of 30 minutes. The catalyst was prepared by combining 10 μmol of (trans, trans-1,4-d? F-i-1, 3-butadiene) of [2,2-propanediol (1-fluoren? L) (cyclopentadiene). ? in? l)] z? rcon? o and 10,000 μmoies, 10 percent MAO in toluene. 35.0 g of syndiotactic propylene were obtained (74.7 percent r pentad by 13 C NMR analysis). Example 43. Preparation of isotactic propylene using (trans, trans-1,4-diphenyl-1,3-butadiene) of rac- [1,2-ethanediibis (1-indenyl)] hafnium and B (C6F5) 3. The general procedure was followed using 715 g of mixed alkanes, hydrogen at 170 kPa, 200 g of propylene monomer and 26 g of ethylene monomer with a polymerization temperature of 70 ° C and a polymerization time of 60 minutes. The catalyst was prepared by combining 5 μmol of (trans, trans-1,4-d? Phen? M, 3-butadiene) of rac- [1,2-ethanediylb? S (1-indenyl)] hafnium and 5 μmol of B (C6F5) 3 in toiuene. 60.7 g of isotactic propylene copolymer (83 percent of mentan was obtained by 13 C NMR analysis). Description of Gas Phase Reactor The gas phase reactions were carried out in a gas-phase fluid bed reactor of 6 liters, having a cylindrical fluidization zone with a diameter of 10 16 cm, 76.2 cm long, and an area of speed reduction of 20.32 cm in diameter and 24.50 cm in length, which is connected by a transition section having tapered walls. The monomers, hydrogen and nitrogen, enter the bottom of the reactor where they pass through a gas distributor plate. The gas flow usually 2 to 8 times at minimum fluidization speed of the solid particles.

Most of the suspended solids are uncoupled in the velocity reduction zone. The reagent gases exit the top of the fluidization zone and pass through a dust filter to remove any particles. The gases then pass through a gas injection pump. No volatile condensation is used. The polymer is allowed to accumulate in the reactor during the course of the reaction. Polymer is removed from the reactor to a recovery vessel by opening a valve located in the lower part of the fiuidization zone. The polymer recovery vessel is maintained at a lower pressure than the reactor. Example 44. Preparation of Ethylene / 1-butene Copolymer Under Gas Phase Polymerization Conditions The catalyst was prepared by impregnating a solution of toluene of 2 μmoles of (trans, trans-1,4-difenbubutadiene) of rac- [1,2 ethanediylbis (1-indenyl)] zirconium and 6 μmol of B (C6F5) 3 in 0.1 grams of Davison ™ 948 silica (available from Davison Chemical Company) which was treated with 1.0 gram of triethylaluminum / gram of silica. The reactor was charged with 1650 KPa of ethylene, 37 KP of 1-butene, 9 kPa of hydrogen and 370 KPa of nitrogen. The reactor temperature was set at 72 ° C and the catalyst was injected. An exotherm was recorded by the injection of the catalyst. The temperature returned to 74 ° C within 3 minutes and the temperature remained stable at 74 ° C for the duration of the operation. 14.3 g of a free flowing polymer powder was recovered after 39 minutes of operation. Example 45: Preparation of Ethylene / Propylene Copolymer having Isotactic Propylene Segments The catalyst was prepared by impregnating a toluene solution of 2 μmol of (trans, trans-1,4-diphenylbutadiene) of rac- [1,2-ethanediylbis (1 -indenyl)] zirconium and 6 μmoles of B (C6F5) 3 in 0.1 grams of Davison'M 948 silica (available from Davison Chemical Company) which was treated with 1.0 gram of triethiumium / gram of silica. The reactor was charged with 650 kPa of propylene, approximately 20 kPa of ethylene, 10 kPa of hydrogen and 290 KPa of nitrogen. The reactor temperature was set at 70 ° C and the catalyst was injected. The temperature remained stable at 70 ° C for the duration of the polymerization. 4.6 g a free flowing isotactic propylene / ethylene copolymer powder was recovered after 60 minutes, (m pentad = 71 percent by lJC NMR analysis).

Example 46: Preparation of (? 4-1-phenyl-1,3-pentadiene) of rac-1, 2-ethanediyl [bis- (1-indenyl)] zirconium In a glove box under inert atmosphere, 0.896 g was combined (2.14 mmoles) of rac-1, 2-ethanediol [(b? S- (1-indenyl)] zirconium dichloride (in 50 ml of toluene) with 0.309 g of 1 -fe n il-1, 3- pentadiene (2.14 mmol), followed by the addition of 1.8 ml of nBuLi (4.5 mmol, in hexane) The color of the reaction changed rapidly to red The reaction mixture was stirred at approximately 25 ° C for 30 minutes followed by heating The product was collected by filtration, the filtrate was concentrated to about 30 ml, and the filtrate was cooled to about -34 ° C for about 18 hours. 0.225 g (21.4 percent) of the reclassified product was asylumized as dark red microcrystals after decanting the mother liquor and drying the product under reduced pressure. ducid The product was identified by 1 H NMR spectrum as (? 4-? f enyl-1,3-pentadiene) of rac-1, 2-ethanediyl [bis- (1-1-indenyl)] zirconium. Example 47 Polymerization of Isotactic Batch Polypropylene Using (? 4-1-phenyl-1,3-pentadiene) of rac- [bis-1, 1 '- (? 5-indenyl) -1,2-ethanediyljzirconium and B ( C6F5) 3 with hydrogen. The general polymerization procedure was followed using 734 g of solvent, hydrogen at 180 kPa, 200 g of propylene monomer with a reaction temperature of 70 ° C and operating time of 30 minutes. The catalyst was prepared by combining 4 μmoles of (? 4-1-phenyl-1,3-pentadiene) of rac- [bis-1, 1 '- (? 5-indenyl) -1,2-ethanediyl] zirconium and 4 μmoles of B (C6F5) 3 in toluene. 82 g of the crystalline polypropylene were obtained. Example 48: Polymerization of Lot Ethylene / Styrene Using (? 4-s-trans-1,4-trans, trans-diphenyl-1,3-pentadiene) of rac- [1,2-ethanediylbis (1-indenyl)] zirconium and B (C6F5) 3 with hydrogen.

The general polymerization procedure was followed using 365 g of solvent, hydrogen at 350 kPa, 458 g of styrene monomer with a reaction temperature of 70 ° C and 1.4 MPa of ethylene on demand and an operating time of 15 minutes. The catalyst was prepared by combining 4 μmoles of (? 4-s-trans-1,4-trans, trans-diphenyl-1,3-pentadiene) of rac-1,2-ethanediyl [bis (1-indenyl)] zirconium and 4 μmol of B (C6Fs) 3 in toluene. 19.8 g of an ethylene / styrene copolymer were isolated. Example 49: Polymerization of Ethylene / Lot 1-octene Using (? -s-trans-1,4-trans, trans-diphenyl-1,3-butadiene) of rac- [1,2-ethanediylbis- (2-methyl) -4-phenyl-indenyl)] zirconium and B (C6F5) 3 with hydrogen. The general procedure was followed using 741 g of solvent, hydrogen at 180 kPa, 129 g of 1-octene monomer with a reaction temperature of 140 ° C and 3.4 MPa of ethylene on demand and an operating time of 15 minutes. The catalyst was prepared by combining 1 μmoles of? 4-s-trans-1,4-trans, trans-diphenyl-1,3-butadiene) of rac- [1,2-ethanediylbis- (2-methyl-4-phenyl- indenyl)] zirconium and 1 μmol of B (C6F5) 3 in toluene. 13.1 g of an ethylene / styrene copolymer were isolated.

Claims

CLAIMS: 1. A metal complex corresponding to the formula: wherein: M is titanium, zirconium or hafnium in the formal oxidation state + 2 or +4; R 'and R "each time they occur, are independently selected from the group consisting of hydrogen, hydrocarbon, silyl, germyl, cyano, halo and combinations thereof, said R' and R" having up to 20 non-hydrogen atoms each, or adjacent R 'groups and / or adjacent R "groups (when R1 and R" are not hydrogen, halo or cyano) together form a bivalent derivative thereby forming a fused ring system; E is silicon, germanium or carbon; x is an integer from 1 to 8; R "independently each time it occurs, is hydrogen or a selected group of silyl, hydrocarbyl, hydrocarbyloxy or combinations thereof, or two R '" groups together form a ring system, said R' "having up to 30 carbon silicon atoms, and D is a stable conjugated diene, optionally substituted with one or more hydrocarbyl groups, silyl groups, hydrocarbon groups, alkyl groups, hydrocarbyl groups, or their mixtures, said D having from 4 to 40 non-hydrogen atoms 2. The complex of claim 1, which is a complex of 1,2-ethanediyl (bis-? S-indenyl) zirconium diene, a complex of 2,2- (cyclopentadienyl) -2- (9-fluorenyl) propanediyl zirconium-diene, a complex of 1,2-ethanediylbis (4-phenyl-1-indenyl) zirconium-diene, a complex of 1,2-ethanediyl bis (2-methyl-4-phenyl-1-indenyl) zirconium- diene, a complex of 1,2-ethanediyl bis (4-naphthyl-1-indenyl) zirconium-diene, a complex of 1,2-ethanediyl bis (2-methyl-4-naphthyl-1-indenii) zirconium-diene, a complex of 1,2-ethanediyl bis (2-methyl-4,7-diphenyl-1-indenyl) zirconium-diene, a complex of 2,2-propanediyl bis (? 5-indenyl) zirconium, a complex of 2,2- propanediyl (cyclopentadienyl-9-fluorenyl) zirconium, a complex of 2,2-propanediyl bis (4-phenyl-1-indenyl) zirconium-diene, a complex of 2,2-propanediyl bis (2-methyl-4-phenyl- 1-indenyl) zirconium-diene, a complex of 2,2-propanediyl bis (4-naphthyl-1-indenyl) zirconium-diene, a complex of 2,2-propanediyl b? S (2-methyl-4,7- diphenyl-1-indenyl) zirconium, a complex of dimethylsilane b? s (2-methyl-4-naphthyl-1-indenyl) zirconium, a complex of bis-2,2-propanediyl (? -indenyl) zirconium-diene, a dimethylsilanediyl (cyclopentadienyl-9-fluorenyl) zirconium-diene complex, a dimethylsilanediyl bis (4-phenyl-1-indenii) zirconium-diene complex, a complex of dimethylsilanediyl bis (2-methyl-4) phenyl-1-indenyl) zirconium-diene, a dimethylsilanediyl bis (4-naphthyl-1-indanyl) zirconium-diene, a dimethylsilanediyl bis (2-methyl-4-naphthyl-1-indenyl) zirconium-diene complex, or a dimethylsilandiyl bis (2-methyl-4,7-diphenyl-1-indenyl) zirconium-diene complex. 3. An ansa-rae complex that has the formula: wherein: M is titanium, zirconium or hafnium in the formal oxidation state + 2; R 'and R "each time they occur, are independently selected from the group consisting of hydrocarbyl hydrogen, silyl, germyl, cyano, halo and combinations thereof, said R' and R" having up to 20 non-hydrogen atoms each one, or adjacent R 'groups and / or adjacent R "groups (when R1 and R" are not hydrogen, halo or cyano) together form a bivalent derivative thereby forming a fused ring system; E is silicon, germanium or carbon; x is an integer from 1 to 8; R '"independently each time it occurs, is hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy or combinations thereof, or two groups R" together form a ring system, said R' "having up to 30 silicon carbon atoms, and D is a stable conjugated diene, optionally substituted with one or more hydrocarbyl groups, silyl groups, hydrocarbylsilyl groups, silylhydrocarbyl groups, or mixtures thereof, said D having from 5 to 40 non-hydrogen atoms. rae that has the formula: or hydrogenated derivatives thereof, wherein: M is titanium, zirconium or hafnium in the formal oxidation state + 2 or +4; R 'and R "each time they occur, are independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R' and R" having up to 20 non-hydrogen atoms each, or adjacent R 'groups and / or adjacent R "groups (when R1 and R" are not hydrogen, halo or cyano) together form a bivalent derivative thereby forming a fused ring system; E is silicon, germanium or carbon; x is an integer from 1 to 8; R '"independently each time it occurs, is hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy or combinations thereof, or two groups R'" together form a ring system, said R "having up to 30 carbon atoms silicon, D is a stable conjugated diene, optionally substituted with one or more hydrocarbon groups, siiio groups, hydrocarbylsilyl groups, silylhydrocarbyl groups, or mixtures thereof, said D having from 4 to 40 atoms that are not hydrogen, and R each time it occurs, is independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl and combinations thereof, said R each having up to 20 non-hydrogen atoms, or adjacent R groups in each separate indenyl system together forming a divalent derivative (i.e. , a hydrocarbonyloyl, siladiyl or germadiyl group) thus forming an additional fused ring 5. The complex of claim 4 wherein: M is zirconium or hafnium in the state d e formal oxidation +2; and D is a stable conjugated diene, optionally substituted with one or more hydrocarbyl groups, silyl groups, hydrocarbylsilyl groups, silylhydrocarbyl groups, or mixtures thereof, said D having from 5 to 40 atoms which are not hydrogen. The complex of claim 1, which is s-trans (4-1,4-trans-trans-diphenyl-1,3-butadiene) of dimethylsilanediyl-bis (2-methyl-4-phenyl) -1- indenyl) zirconium, s-trans (? 4-1,4-trans-trans-diphenyl-1,3-butadiene) of dimethylsilanediyl-bis (2-metii-4- (1-naphthyl)) - 1 ~ indenyl) zirconium , s-rans (? 4-1, 4-trans-trans-diphenyl-1,3-butadiene) of 1,2-ethanediyl-bis (2-methyl-4- (1-phenyl) -1-indenyl) zirconium , s-trans (? 4- 1, 4-trans-trans-diphenii-1,3-butadiene) of 1,2-ethanediyl-bis (2-methyl-4- (1-naphthyl) -1-indenyl) zirconium , s-trans (? -trans, trans-1,4-diphenyl-1,3-butadiene) of [1,2-ethandiylbis (1-indenyl)] zirconium, s-trans (? 4-trans, trans-1 , 4-diphenyl-1,3-butadiene) of [1,2-ethaned? Ilb? S (1-tetrahydroindenyl)] -zirconium, s-trans (? 4-trans, trans-1 * 4-diphenyl-1 , 3-butadiene) of [1,2-ethanediylbis (1-indenyl)] hafnium, and (trans, trans, -1, 2-diphenyl-1,3-butadiene) of [2,2-propanediyl (9-fluorenyl ) - (cyclopentadienyl)] zirconium. 7. The process for preparing a transition metal complex having the formula: CpCp'MD wherein: M is titanium, zirconium or hafnium in the formal oxidation state + 2 or +4. Cp and Cp 'are each groups of substituted or substituted cyclopentadienyl being substituted with one to five substituents independently selected from the group consisting of hydrocarbyl, silyl, germyl, halo, cyano, hydrocarbyloxy, and mixtures thereof, said substituent having up to 20 atoms which are not of hydrogen, or optionally, two of said different substituents, cause Cp or Cp 'to have a fused ring structure, or wherein a substituent in the Cp and Cp' forms form a loop portion joining Cp and Cp '; and D is a stable, conjugated diene of 4 to 40 carbon atoms by reacting the following components in any order: 1) a complex of the formula: CpCp'M * X or CpCp'M ** X2 wherein; Cp and Cp 'are as previously defined; M * is a titanium, zirconium or hafnium in the formal +3 oxidation state; M ** is titanium, zirconium or hafnium in the formal oxidation state +4; and X is a hydrocarbyl group of C? -6, halide, Ci hydrocarbyloxy. 6 or C? .6 hydrocarbylamide; 2) a diene corresponding to the formula, D; and 3) optionally when X is C1.6 hydrocarbyl, otherwise, not optionally, a reducing agent and recovering the complex containing the resulting diene. The process of claim 7, wherein the starting compound comprises a mixture of rae- and meso-diastereomers and the resulting transition metal-diene complex essentially lacks the meso-diastereomer. 9. The process of claim 7, wherein the starting compound comprises a mixture of or hydrogenated derivatives thereof, wherein, M and X are as previously defined in claim 7, E is silicon or carbon; x is from 1 to 8; R "is selected from the group consisting of hydrogen, methylbenzyl, tertbutyl or phenyl, and R each time it is presented is independently selected from the group consisting of hydrocarbyl hydrogen, silyl, germium and combinations thereof, said R, having up to 20 atoms that are not hydrogen, each one or adjacent R groups in each separate indenyl system, together form a divalent derivative thereby forming an additional fused ring 10. A process for preparing an ansa-rae transition metal complex that has the formula: wherein: M is titanium, zirconium or hafnium; R independently each time it is presented is selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and sus. combinations, or the adjacent R groups together form divalent derivatives thereby forming a fused ring; E is silicon or carbon; x is from 1 to 8; R '"independently each time it occurs, is hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, or two R'" groups together form a ring system, said R '"having up to 30 carbon atoms or silicon, and X is halide, by reacting the following components in any order: 1) a mixture of rae- and meso-diastereomers of a compound having the formula: wherein: M, X, E, x, and R '"are as previously defined, and X * is a hydrocarbyl group of C? .6, halide, hydrocarbyloxy of C? -6, or di-hydrocarbylamide of C1" 6; 2) a diene corresponding to formula D; and 3) optionally when X is C1-6 hydrocarbyl, somehow not optionally, a reducing agent to form a rac-diene ansa-containing complex corresponding to the formula wherein, M, E, x, R, R '"and D are as previously defined, 2) contacting the rac-diene ansa complex with a halogenating agent, and 5) recovering the resulting complex. The process of claim 10, wherein the starting compound comprises a mixture of rae- and meso-diastereomers of a metal complex having the formula or hydrogenated derivatives thereof, wherein M and X are as previously defined in claim 10; E is silicon or carbon; x is from 1 to 8; R "is selected from the group consisting of hydrogen, methyl benzyl, terbutyl or phenyl, and R independently each time it is presented is selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, or the adjacent R groups together form divalent derivatives thus forming a fused ring 12. compositions of matter useful as olefin polymerization catalysts comprising: 1) a metal complex containing two cyclopentadienyl groups or substituted cyclopentadienyl groups, said compound corresponding to the formula : CpCp'MD wherein: M is titanium, zirconium or hafnium in the formal oxidation state +2 or +4; Cp and Cp 'are each substituted or substituted cyclopentadienyl groups bonded in a? 5 -linking mode to the metal, said substituted cyclopentadienyl group being substituted with one to five substituents independently selected from the group consisting of hydrocarbyl, silyl , germyl, haio, cyano, hydrobiioxy, and mixtures thereof, said substituent having up to 20 non-hydrogen atoms, or optionally, two of said substituents (except cyano or halo) together, cause Cp or Cp 'to have a structure of fused ring, or wherein a substituent in the forms Cp and Cp 'form a loop portion joining Cp and Cp', D is a stable, conjugated diene, optionally substituted with one or more hydrocarbyl groups, silyl groups, hydrocarbylsilyl groups, silylhydrocarbyl groups, or mixtures thereof, said D having from 4 to 40 atoms which are not hydrogen and forming a p-complex with M when M is in the formal oxidation state +2, and forming a s-complex with M, when M is in the formal oxidation state +4; said complex having been activated by the use of: 2) a cocatalyst or activation technique selected from the group consisting of: 2a) strong Lewis acids; 2b) oxidation salts corresponding to the formula: (Oxe +) d (Ad-) e where: Oxe + is a cationic oxidizing agent having a charge of e +; e is 1 or 2; and A is a non-coordinating compatible anion that has a charge of d-; d is an integer from 1 to 3; 2c) carbenium salts corresponding to the formula:c + A "where: c + is a carbenium ion of C1-20, and A 'is a non-coordinating compatible ion having a charge of •1; 2d) an activation technique comprising electrolyzing the metal complex under mass electrolysis conditions in the presence of an electrolyte of the general formula: G + A "wherein A- is a non-coordinating compatible anion having a charge of -1; and G + is a cation that is not reactive towards the starting and resulting complex; 2e) polymeric or oligomeric alumoxanes; 2f) salts of a siinium ion and a non-coordinating compatible anion represented by the formula: R # 3 Si (X #) s + A "where: R # is a hydrocarbyl of C ^ o, s is 0 or 1, X # is a neutral Lewis base, A" is as previously defined, and 2g) salts of Bronsted acid having the formula: ( LH) -d (Ajen where: L is a neutral Lewis base; (L-H) 'is a Bronsted acid; Ad "is a compatible, non-coordinating anion, which has a charge of d-, and d is an integer from 1 to 3, as long as the cocatalyst is an acid salt of Bronsted 2g), D is a stable conjugated diene of 5 to 40 carbon atoms p-linked to the transition metai; and M is titanium, zirconium or hafnium in the formal oxidation state +2. 13. The composition of matter of claim 12, wherein the metal complex corresponds to the formula: wherein: M is titanium, zirconium or hafnium, preferably zirconium or hafnium, in the formal oxidation state +2 or +4; R 'and R "each time they occur, are independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R' and R" having up to 20 non-hydrogen atoms each, or adjacent R 'groups and / or adjacent R "groups (when R' and R" are not hydrogen, halo or cyano) together form a bivalent derivative or an R 'and an R "(when the R' and R "are not hydrogen, halo or cyano) combine together to form a divalent radical by joining the two substituted cyclopentadienyl groups; and D is as previously defined in claim 12. 14. The composition of claim 12; wherein the cocatalyst is a strong Lewis acid selected from Group 13 compounds substituted with C1.30 hydrocarbyl, Group 13 compounds substituted with halogenated C1.30 hydrocarbyl; amine, phosphine, aiiphatic alcohol, and mercaptan adducts of Group 13 compounds substituted with C 1 or halogenated hydrocarbyl and combinations thereof. 15. The composition of claim 14, wherein the strong Lewis acid is tris (pentafluorophenyl) borane. 16. The composition of claim 14, further comprising a polymeric or oligomeric alumoxane. 17. The composition of claim 14, further comprising hydrogen or ethylene. 18. The composition of claim 13, wherein M is zirconium or hafnium in the formal oxidation state +2 and the diene are attached to the metal by a complex structure. The composition of claim 18, wherein E is a 1,3-butadiene which is terminally substituted with one or two hydrocarbyl groups of C? -? 0. The composition of claim 18, wherein the diene is 1,4-diphenylbutadiene or 1,4-ditolylbutadiene. The composition of claim 18, wherein the cocatalyst is tris (pentafluorophenyl) borane. 22. The composition of claim 21, further comprising a polymeric and oligomeric alumoxane. The composition of claim 17, wherein M is zirconium or hafnium in the formal +4 oxidation state and the diene is attached to the metal by an s-complex structure and is in the s-cis configuration. The composition of claim 23, wherein D is 1,3-butadiene or a 1,3-butadiene substituted in the 2 or 3 position with one or two hydrocarbyl groups of C1.10. The composition of claim 24, wherein the diene is isoprene or 2,3-dimethylbutadiene. 26. The composition of claim 23, wherein the cocatalyst is tris (pentafluorophenyl) borane. 27. The composition of claim 26, further comprising polymeric or oligomeric alumoxane. The composition of claim 12, obtained by combining a diene complex with a Bronsted acid salt wherein the diene complex has the formula: wherein: M is titanium, or hafnium in the formal oxidation state +2; R 'and R "each time they occur, are independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R' and R" having up to 20 non-hydrogen atoms each, or adjacent R 'groups and / or adjacent R "groups (when R' and R" are not hydrogen, halo or cyano) together form a bivalent derivative or an R 'and an R "combine together to form a divalent radical linking the two substituted cyclopentadienyl groups, and D 'is a conjugated diene having from 5 to 40 carbon atoms which is attached to the metal, and the Bronsted acid salt has the formula: wherein: L is a neutral Lewis base, (LH) is a Bronsted acid, B is boron, and Q 'is a fluorinated hydrocarbyl group of C? -20 29. The composition of claim 28, wherein (BQ') is borate of tetrakispentafluorophenyl, M 'is zirconium and hafnium and the diene is 2,4-hexadiene, 1-phenyl-1,3-pentadiene, 1,4-diphenium lbutadiene or 1,4-ditolylbutadiene. The composition of claim 12, wherein the metal complex is a diene complex of 1,2-ethanediyl (bis-? 5-indenyl) zirconium, a complex of 2,2- (cyclopentadienyl) -2- ( 9-fluorenyl) propanediyl zirconium-diene, a complex of 1,2-ethanediylbis (4-phenyl-1-indenii) zirconium-diene, a complex of 1,2-ethanediyl bis (2-methyl-4-phenyl-1- indenyl) zirconium-diene, a complex of 1,2-ethanediyl bis (4-naphthyl-1-indenyl) zirconium-diene, a complex of 1,2-ethanediyl bis (2-methyl-4-naphthyl-1-indenyl) zirconium-diene, a complex of 1,2-ethanediyl bis (2-methyl-4,7-difeni! -1-indeni!) z? rconium-diene, a complex of 2,2-propanediyl bis (? -indenyl) zirconium, a complex of 2,2-propanediyl (cyclopentadienyl-9-fluorenyl) zirconium, a complex of 2,2-propanediyl bis (4-phenyl-1-indenyl) zirconium-diene, a complex of 2,2-propanediyl bis (2-methyl-4-phenyl-1-indenyl) zirconium-diene, a complex of 2,2-propanediyl bis (4-naphthyl-1-indenyl) zirconium-diene, a complex of 2,2-propanediii bis (2 -methyl-4,7-diphenyl-1-indenyl) zi rconium, a dimethylsilane bis (2-methyl-4-naphthyl-1-indenyl) zirconium complex, a bis-2,2-propanediyl (? s-indenyl) zirconium-diene complex, a dimethylsilanediyl (cyclopentadienyl-9- fluorenyl) zirconium-diene, a dimethylsilynediyl bis (4-phenyl-1-indenyl) zirconium-diene complex, a dimethylsilanediyl bis (2-methyl-4-phenyl-1-indenyl) zirconium-diene complex, a dimethylsilanediyl bis (4-naphthyl-1-indanyl) zirconium-diene, a dimethylsilanediyl bis (2-methyl-4-naphthii-1-indenyl) zirconium-diene complex, or a dimethylisilanodiyl biss complex (2-metii-4,7- diphenii-1-indenyl) zirconium-diene. The composition of claim 12, wherein the metal complex has the formula: wherein: M is titanium, zirconium or hafnium in the formal oxidation state +2 or +4; R 'and R "each time they occur are independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, or adjacent R' groups and / or adjacent R" groups formed together a bivalent derivative thus forming a fused ring system; E is silicon, germanium or carbon; x is an integer from 1 to 8; R "'is selected from the group consisting of hydrogen, methyl, benzyl, tertbutyl or phenyl, and D is a stable conjugated diene of 5 to 40 carbon atoms. 32. The composition of claim 31, wherein the metal complex is a rae-metal amphase complex. The composition of claim 12, wherein the metal complex is s-trans (? 4-1, 4-trans, trans-diphenyl-1,3-butadiene) of bis (? 5-cyclopentadienyl) zirconium, s -cis (2,3-dimethyl-1, 3-butadiene) of bis (cyclopentadienyl) zirconium, is s-trans (? 4-1, 4-trans, trans-diphenyl-1,3-butadiene) of dimethylsilanediyl-bis ((2-methyl-4-phenyl) -1-indenyl) zirconium, is s-trans (? 4-1, 4-trans, trans-diphenyl-1,3-butadiene) of dimethylsilanediyl-bis ((2-methyl-4-1- (1-naphthyl)) - 1-indenyl) zirconium, is s- trans (? 4-1, 4-trans, trans-diphenyl-1,3-butadiene) of 1,2-ethanediyl-bis (2-methyl-4- (1-phenyl) -1-indenyl) zirconium, is s-trans (? 4-1, 4-trans, trans-diphenyl-1,3-butadiene) of 1,2-ethanediyl-bis (2-methyl-4- (1-naphthyl) -1-indenyl) zirconium, is s-trans (? 4-1, 4-trans, trans-diphenyl-1,3-butadiene) [1,2-ethanediylbis (1-indenyl) zirconium, is s-trans (? 4-1, 4-trans, trans-diphenyl-1,3-butadiene) of [1,2-ethanediylbis (1-tetrahydroindenyl) ] zirconium, is s-trans (? 4-1, 4-trans, trans-diphenyl-1, 3-butadiene) of [1,2-ethanediylbis (1-indenyl)] hafnium, or is (trans, trans-1) , 4-diphenyl-1,3-butadiene) of [2,2-propanediyl (9-fluorenyl) - (cyclopentadienyl)] zirconium. 34. A metallic complex corresponding to the two zwitterionic structures in equilibrium of the formula: CpCp '• M M + CR3 CR5R6 \ X CR? R2 CR4 (BQ-)' CR ^ «6 CpCp 'M C 1R2 where: M is titanium, zirconium or hafnium in the formal oxidation state + 4; Cp and Cp 'are each groups of substituted or substituted cyclopentadienyl being substituted with one to five substituents independently selected from the group consisting of hydrocarbyl, silyl, germyl, halo, cyano, hydrocarbyloxy, and mixtures thereof, said substituent having up to 20 atoms which are not of hydrogen, or optionally, two of said substituents together, cause Cp or Cp "to have a fused ring structure, or wherein a substituent in the Cp and Cp 'forms form a loop portion joining Cp and Cp Q, independently each time it is presented, is selected from hydride, dialkylamido, halide, alkoxide, aryioxide, hydrocarbyl, and halo-substituted hydrocarbyl radicals, said Q having up to 20 carbon atoms with the proviso that in more than one presentation, Q is halide, Ri, 2, R3, R4, Rs, e, are independently hydrogen, hydrocarbyl, silyl and combinations thereof, each of said R1 to R6 having ta 20 atoms that are not hydrogen and B is boron in a valence state of 3. 35. A metal complex according to claim 34, corresponding to the formula: wherein: Ri, R2, s and e are hydrogen; R3 and R are hydrogen, C3-4 alkyl or phenyl, M is zirconium in the formal oxidation state +4, and R 'and R "each time they occur, are independently selected from the group consisting of hydrogen, hydrocarbyl , silyl, germyl, cyano, halo and combinations thereof, said R 'and R "having up to 20 non-hydrogen atoms each, or adjacent R' groups and / or adjacent R" groups (when R 'and R " they are not hydrogen, halo or cyano) together form a divalent derivative combine to form a divalent radical (when R 'and R "are not hydrogen, halo or cyano) by linking the two cyclopentadienyl groups 36. A metal complex according to Claim 34, corresponding to the formula: wherein: M is zirconium in the formal oxidation state +4; R1 R2, Rs and e are hydrogen; R3 and R are hydrogen or methyl; and R 'and R "each time they occur, are independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R' and R" each having up to 20 atoms that they are not hydrogen, or the adjacent R 'groups and / or adjacent R "groups (wherein R' and R" are not hydrogen, halo or cyano) together form a divalent derivative or an R 'and an R "together (when the groups R 'and R "are not hydrogen, halo or cyano), combine to form a divalent radical by ligating the two cyclopentadienyl groups. 37. An olefin polymerization process comprising contacting at least one α-olefin having from 2 to 10 carbon atoms under polymerization conditions with a composition according to any of claims 12 to 36. 38. The The process of claim 37, wherein the metal complex corresponds to the formula: wherein: M is zirconium or hafnium, in the formal oxidation state +2 or +4; R 'and R "each time they occur, are independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R' and R" having up to 20 non-hydrogen atoms each, or adjacent R 'groups and / or adjacent R "groups (when R' and R" are not hydrogen, halo or cyano) together form a bivalent derivative or an R 'and an R "(when the R' and R "are not hydrogen, halo or cyano) combine together to form a divalent radical by joining the two substituted cyclopentadienyl groups; and D is as previously defined in claim 12. 39. The process of claim 37, wherein the cocatalyst is a strong Lewis acid selected from Group 13 compounds substituted with C? -30 hydrocarbyl, Group 13 compounds substituted with halogenated C?. 3 hydrocarbyl; amine, phosphine, aliphatic alcohol, and mercaptan adducts of Group 13 compounds substituted with halogenated C? .30 hydrocarbyl and combinations thereof. 40. The process of claim 37, wherein the strong Lewis acid is tris (pentafluorophenyl) borane 41. The process of claim 39, wherein the polymeric or oligomeric alumoxane is additionally present. 42. The process of claim 39, wherein hydrogen or ethylene are present in the polymerization. 43. The process of claim 38, wherein M is zirconium or hafnium in the formal oxidation state +2 and the diene is bonded to the metal by a structure. 44. The process of claim 43, wherein E is a 1,3-butadiene which is terminally substituted with one or two hydrocarbyl groups of C6-? O- 45. The process of claim 43, wherein the diene is 1 , 4-diphenylbutadiene or 1,4-ditolylbutadiene. 46. The process of claim 43, wherein the cocatalyst is tris (pentafluorophenyl) borane. 47. The process of claim 46, wherein a polymeric or oligomeric alumoxane is additionally present. 48. The process of claim 37, wherein M is zirconium or hafnium in the formal +4 oxidation state and the diene is bound to the metal by an s-complex structure and is in the s-cis configuration. 49. The process of claim 48, wherein d is 1,3-butadiene or a 1,3-butadiene substituted in the 2 or 3 position with one or two hydrocarbyl groups of C ^ o- 50. The process of the claim 49, wherein the diene is isoprene or 2,3-dimetiibutadiene. 51 The process of claim 50, wherein the cocatalyst is tris (pentafluorophenyl) borane. 52. The process of claim 51, wherein a polymeric or oligomeric alumoxane is additionally present. 53. The process of claim 37, wherein the catalyst is obtained by combining a diene complex with a Bronsted acid salt wherein the diene complex has the formula wherein: M is zirconium or hafnium in the formal oxidation state +2; R 'and R "each time they occur, are independently selected from the group consisting of hydrogen, hydrocarbyl, siiyl, germyl, cyano, halo and combinations thereof, said R' and R" having up to 20 non-hydrogen atoms each, or adjacent R 'groups and / or adjacent R "groups (when R' and R" are not hydrogen, halo or cyano) together form a bivalent derivative or an R 'and an R "combine together to form a radical divalent linking the two substituted cyclopentadienyl groups, and D 'is a conjugated diene having from 5 to 40 carbon atoms that is p-bound to the metai; and the Bronsted acid salt has the formula: (LH) + (BQ '4) -where: L is a Lewis neutral base, (LH) + is a Bronsted acid, B is boron, and Q' is a fluorinated hydrocarbyl group of C1.20 54. The process of claim 53 , wherein (BQ!) is tetrakispentafluorophenyl borate, M 'is zirconium and hafnium and the diene is 2,4-hexadiene, 1-phenyl-1,3-pentadiene, 1,4-dif enylbutadiene or 1,4-ditolylbutadiene. 55. The process of claim 37, wherein the metal complex is a diene complex of 1,2-ethanediyl (bis-? 5-indenyl) zirconium, a complex of 2,2- (cyclopentadienyl) -2- ( 9-fluorenyl) propanediyl zirconium-diene, a complex of 1,2-ethanediylbis (4-phenyl-1-indenyl) zirconium-diene, a complex of 1,2-ethanediyl bis (2-methyl-4-phenyl-1- indenyl) zirconium-diene, a complex of 1,2-ethanediyl bis (4-naphthyl-1-indenii) zirconium-diene, a complex of 1,2-ethanediyl bis (2-methyl-4-naphthyl-1-indenyl) zirconium-diene, a complex of 1,2-ethanediyl bis (2-methyl-4,7-diphenyl-1-indenii) zirconium-diene, a complex of 2,2-propanediyl bis (? 5-indenyl) zirconium, a a complex of 2,2-propanediyl (cyclopentadienyl-9-fluorenyl) zirconium, a complex of 2,2-propanediyl bis (4-phenyl-1-indenyl) zirconium-diene, a complex of 2,2-propanediyl bis ( 2-methyl-4-phenyl-1-indenyl) zirconium-diene, a complex of 2,2-propanediyl bis (4-naphthyl-1-indenyl) zirconium-diene, a complex of 2,2-propanediyl bis (2- methyl-4,7-diphenyl-1-indenyl) zircon io, a dimethylsilane bis (2-methyl-4-naphthyl-1-indenyl) zirconium complex, a bis-2,2-propanediyl (? 5-indenyl) zirconium-diene complex, a dimethylsilanediyl (cyclopentadienyl-9- fluorenyl) zirconium-diene, a complex of dimethylsiian-diyl bis (4-phenyl-1-indenyl) zirconium-diene, a complex of dimethylsilanediii bis (2-methyl-4-phene-1-indenyl) zirconium-diene, a dimethylsilanediyl bis ( 4-naphthyl-1-indanyl) zirconium-diene, a dimethylsilanediyl bis (2-methyl-4-naphthyl-1-indenyl) zirconium-diene complex, or a dimethylsilanediyl bis (2-methyl-4,7-diphenyl- 1-indenyl) zirconium-diene. 56. The process of claim 37, wherein the metal complex has the formula: wherein: M is titanium, zirconium or hafnium in the formal oxidation state +2 or +4; R 'and R "each time they occur are independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, or adjacent R' groups and / or adjacent R" groups formed together a bivalent derivative thus forming a fused ring system; E is silicon or carbon; x is an integer from 1 to 8; R '"is selected from the group consisting of hydrogen, methyl, benzyl, tertbutyl or phenyl, and D is a stable conjugated diene of 5 to 40 carbon atoms. 57. The process of claim 56, wherein the metal complex is a rae-metal complex. 58. The process of claim 37, wherein the metal complex is s-trans (? -1,4-trans, trans-diphenyl-1,3-butadiene) of bis? '- cyclopentadienyljzirconium, s-cis (2). , 3-dimethyl-1,3-butadiene) of bis (cyclopentadienyl) zirconium, is s-trans (? 4-1, 4-trans, trans-diphenyl-1,3-butadiene) of dimethylsilanediyl-bis ((2- methyl-4-phenyl) -1-indenyl) zirconium, is s-trans (? -1,4-trans, trans-diphenyl-1,3-butadiene) of dimethylsilanediyl-bis ((2-methyl-4-1- (1-naphthyl)) - 1-indenyl) zirconium, is s- trans (? 4-1,4-trans, trans-diphenyl-1,3-butadiene) of 1,2-ethanediyl-bis (2-methyl- 4- (1-phenyl) -1-indenyl) zirconium, is s-trans (? -1,4-trans, trans-diphenyl-1,3-butadiene) of 1,2-ethanediyl-bís (2-methyl- 4- (1-naphthyl) -1-indenyl) zirconium, is s-trans (? -1,4-trans, trans-diphenyl-1,3-butadiene) of [1,2-ethanediylbis (1-indenyl) zirconium , is s-trans (? 4-1, 4-trans, trans-diphenyl-1,3-butadiene) of [1,2-ethanediylbis (1-tetrahydroindenyl)] zirconium, is s-trans (? 4-1, 4-trans, trans-diphenyl-1,3-butadiene) of [1,2-ethanediylbis (1- indenyl)] hafnium, or is (trans, trans-1,4-diphenyl-1,3-butadiene) of [2,2-propanediyl (9-fluorenyl) - (cyclopentadienyl)] zirconium. 59. A process according to claim 37, wherein the metai complex has the formula: where: M is titanium, zirconium or hafnium in the formal oxidation state + 2; R 'and R "each time they occur are independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, or adjacent R' groups and / or adjacent R" groups formed together a bivalent derivative thus forming a fused ring system; E is silicon, germanium or carbon; x is an integer from 1 to 8; R "" each time it occurs independently, is hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, or two groups R '"together form a ring system, said R'" having up to 30 carbon atoms or silicon; D is a stable conjugated diene of 5 to 40 carbon atoms. 60. The process of claim 39 wherein M is zirconium or hafnium in the formal oxidation state +2. 61. The process of claim 37, wherein the complex is a rasa-metal ansa complex having the formula wherein: M is titanium, zirconium or hafnium in the formal oxidation state +2; R 'and R "each time they occur are independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, or adjacent R' groups and / or adjacent R" groups formed together a bivalent derivative thus forming a fused ring system; E is silicon, germanium or carbon; x is an integer from 1 to 8; R '"each time it occurs independently, is hydrogen or a selected group of silyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, or two groups R'" together form a ring system, said R '"having up to 30 carbon atoms or yes licio, D is a stable conjugated diene of 5 to 40 carbon atoms. 62. The process of claim 59, wherein the metal complex is a rae-metal ansa complex having the formula: or hydrogenated derivatives thereof, wherein: M is zirconium or hafnium in the formal oxidation state +2; E is silicon or carbon; x is from 1 to 8; R "is selected from the group consisting of hydrogen, methyl benzyl, terbutyl or phenyl, and R each time it is presented, is independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl and combinations thereof, said R having each one to 20 atoms that are not hydrogen, or adjacent R groups in each separate indenyl system together form a divalent derivative (i.e., a hydrocarbyldiyl, siladiyl or germadiyl group) thereby forming a fused additional ring. 63. The process of claim 37, wherein the olefin is propylene. 64. The process of claim 37, wherein a combination of ethylene is polymerized with one or more monomers selected from the group consisting of propylene, 1-butene, 1 -hexene, 1-ketene, styrene, ethylidene norbornene, piperylene, and 1, 4-hexadiene. 65. The process of claim 37 wherein the catalyst is supported. 66. The process of claim 65, which is a gas phase polymerization. 67. The process of claim 66, which incorporates recycling the condensed monomers or solvent.