MXPA99012042A - Catalyst activator - Google Patents

Abstract

A catalyst activator particularly adapted for use in the activation of metal complexes of metals of Group 3-10 for polymerization of ethylenically unsaturated polymerizable monomers, especially olefins, comprising two Group 13 metal or metalloid atoms and a ligand structure including at least one bridging group connecting ligands on the two Group 13 metal or metalloid atoms.

Description

CATALYTIC ACTIVATOR DESCRIPTION OF THE INVENTION The present invention relates to compounds that are useful as catalyst components. More particularly, the present invention relates to said compounds which are particularly adapted for use in the coordination polymerization of unsaturated compounds comprising two metal atoms of Group 13 or metalloids and a ligand structure that includes at least one bridging group connecting ligands on their two metal atoms of Group 13 or metalloids. Such compounds are particularly advantageous for use in a polymerization process, wherein the catalyst, the catalyst activated and at least one polymerizable monomer are combined under polymerization conditions to form a polymeric product. Previously, it is known in the art to activate Ziegler-Natta polymerization catalysts, particularly such catalysts comprising Group 3-10 metal complexes containing aplocated, delocalised ligand groups through the use of Bronsted acid salts capable of transferring a proton to form a cationic derivative or other catalytically active derivative of said metal complex of Group 3-10. Preferred Bronsted acid salts are such compounds that contain a cation / anion pair that is capable of making the metal complex of Group 3-10 catalytically active. Suitable activators include fluorinated aryl borate anions, preferably tetrakis (pentafluorophenyl) borate anions. Additional suitable anions include sterically protected diboro anions corresponding to the formula: cs2 wherein: S is hydrogen, alkyl, fluoroalkyl, aryl or fluoroaryl, ArF is fluoroaryl, and X1 is either hydrogen or halide, described in US-A-5,447,895. Additional examples include carborane compounds such as described and claimed in US-A-5,407,884. Additional bisborane compounds, which lack aromatic bridging groups, have been previously described in US-A-5,496,960, Anaew. Chem. Int. Ed. Enql. (1995) 34 (7), 809-11, Polvhedron. (1997), 17 (1), 119-124, Orqanometallics, (1994), 13 (10) 3755-7, Aust. J. Chem .. (1979), 32 (11), 2381-93 and Spectrochim. MINUTES. PART A. (1968), 24 (8), 1125-33. Examples of preferred charge release activators (cation / anion pair) are ammonium, sulfonium or phosphonium salts capable of transferring a hydrogen ion, described in US-A-5, 198,401, US-A-5,132,380, US-A- 5,470,927 and US-A-5, 153, 157, as well as oxidation salts such as salts of carbonium, ferrocenium and silylium, described in US-A-5,350,723, US-A-5, 189, 192 and US-A-5,625,087 . Other suitable activators for the above metal complexes include strong Lewis acids including (trisperfluorophenyl) borane and tris (perfluorobiphenyl) borane. The initial composition has previously been described for the end use set forth in EP-A-520,732, while the latter composition is similarly described by Marks, et al., In J. Am. Chem. Soc. 118, 12451-12452 (1996 ). Despite the satisfactory operation of the above catalyst activators under a variety of polymerization conditions, there remains a need for improved cocatalysts to be used in the activation of various metal complexes under a variety of reaction conditions. Accordingly, it could be desirable if catalyst activators are provided which can be employed in solution, slurry, gas phase or high pressure polymerizations and under homogenous or heterogeneous process conditions having improved activation properties. According to the present invention, there are now provided compounds containing the group 13 useful as catalyst activators in neutral (Lewis acid) or separately charged form (cation / anion pair), corresponding to the formula: (Z *) z wherein: B1 and B2 independently of each occurrence are metal atoms of Group 13 or metalloids, preferably boron; Z * is an optional divalent bridge group containing from 1 to 20 atoms, not representing hydrogen atoms; R1 and R2 independently of each occurrence are anionic, monovalent ligand groups, containing from 1 to 40 atoms, not representing hydrogen atoms, and, for cationic compounds, further comprising a dissociated cation portion; Arf1 and Arf2 independently of each occurrence are fluorinated, monovalent organic groups containing from 6 to 100 carbon atoms, an Arf1 group and a R2 group, or an Arf2 group and a R1 group together form a divalent bypass group, and optionally also one group Arn and one group Arf2 together form a divalent bridge group of C6-? oo, z is 0 or 1, rys independently are 0, 1 or 2, and m and n are 1, 2 or 3; provided that when z is 0, at least one of Arf1 and Arf2 are joined together, and the sum of r, z and m is 3 or 4, in B1 of the initial event it is neutral and in B1 of the final event it is negatively charged, this load being balanced by a cation component of an R1; and the sum of s, z and n is 3 or 4, in B2 of initial event is neutral and in B2 of final event is negatively charged, said load being balanced by a cation component of R2. Further, according to the present invention, there is provided a catalyst composition for polymerizing a polymerizable, ethylenically unsaturated monomer comprising, in combination, the above-described compound and a metal complex of Group 3-10, or the resulting reaction prt of said combination. In addition, according to the present invention, there is provided a process for the polymerization of one or more polymerizable, ethylenically unsaturated monomers comprising contacting them, optionally in the presence of an aliphatic hydrocarbon, to the inert icicic or aromatic, with the catalyst composition described above. The above compounds are only adapted for use in the activation of a variety of metal complexes, especially Group 4 metal complexes, under standard and atypical olefin polymerization conditions. They are only capable of forming monomeric and dimeric cationic metal complexes when combined with neutral metallocene complexes under said polymerization conditions. Due to this fact, the above compounds are capable of forming highly desirable olefin polymers having improved levels of long chain branching, stereospecific character and comonomer distribution. In particular, the bis-anions, due to the even form of the active catalyst sites very close to each other, are capable of providing a higher local concentration of the site of the active catalyst at the point of polymer formation. In addition, said catalyst sites in pairs may be composed of two different metal or metal ligand arrangements, or otherwise be formed to provide desirable polymer properties. For example, the use of symmetric or non-symmetric bis-anions results in two catalytically active sites that are kept in close proximity during a polymerization reaction, thus providing a large increase in the local concentration of the active catalyst sites. This increased local concentration of active catalyst sites leads to an improved stereostructure, molecular weight and microstructure of the polymer. Certain nearby catalyst sites result in the random incorporation of comonomer, others affect the stereospecific character of their closest neighbors. By controlling the random versus aggregated distribution of the comonomer, block or non-block copolymers can be prepared. In addition, the two catalysts associated with each bis-anion by themselves may be non-specific or stereospecific, so that the resulting combination catalyst is adapted to pre block copolymers via polymer exchange between said non-specific and stereospecific catalysts. The degree of long chain branching in polyolefins pred using multiple catalyst sites in bis-anions is improved due to the rate of reincorporation of the vinyl-terminated macromonomer generated in situ in the developing polymer chain due to the local concentration of further catalyst. high.

DETAILED DESCRIPTION OF THE INVENTION All references herein to the elements belonging to a certain Group refer to the Periodic Table of the Elements published and registered by CRC Press, Inc., 1995. Also, any reference to the Group or Groups must be to the Group or Groups as reflect in this Periodic Table of the Elements using the IUPAC system to list groups. When, in reference to a cation portion of any compound herein, it is stated that a ligand group comprises said cation, it should be understood that the cation is not chemically or physically incorporated into said ligand, or chemically necessary form attached to the same, in view of the fact that the cation can be dissociated freely from the anion portion of the compound. Rather, said ligand group is said to "comprise" the cation in order to properly represent the correct nr of cations as dictated by the load balancing considerations. The catalyst activators of the invention are further characterized in the following manner. The preferred metal or Group 13 metalloids include aluminum and boron. Highly preferred, both B1 and B2 are boron. The cocatalysts can be neutral Lewis acids or salts comprising one or more cation-anion pairs. Examples of suitable neutral Lewis acids according to the present invention correspond to the formula: (R2) * - (Ar ^ n where all the variables are as previously defined, and the sum of r, z and m and the sum of s, z, and n, both are 3. More specific examples of the above Lewis acid compounds correspond to the formula: wherein: R1 and R2 independently of each occurrence are hydrocarbyl of C? _20, halohydrocarbyl or halocarbyl, and Arf1-Arf2 in combination, independently of each occurrence, is an aromatic group substituted with fluoro, divalent of 6 to 20 carbons. Preferred examples of the above Lewis acid compounds are the following: Examples of separate charge compounds suitable in accordance with the present invention correspond to the formula: f2 (R2) s B ^ (Ar) n wherein: R1 and R2 independently of each occurrence are hydrocarbyl groups of C? 20, halohydrocarbyl, or halocarbyl, and (when the sum of r, z and m is 4) one of R1 further comprises a cation selected from the group consisting of cations protons of Bronsted acids, ferrocenium cations, carbonium cations, silylium cations and Ag +, and (when the sum of s, zyn is 4) one of R2 also comprises a cation selected from the group consisting of protonated cations of Lewis acids , ferrocenium cations, carbonium cations, silylium cations and Ag +; rys are 0, 1 or 2, provided that at least one of r and r is not 0, and the sum of r, z and m is 3 or 4 and the sum of s, z and n is 3 or 4, provided that at least one of the above sums are 4. More specific examples of the above separate charge compounds correspond to the formula: wherein: R1 and R2 independently of each occurrence are C1- or hydrocarbyl groups, halohydrocarbyl or halocarbyl, and (when connected to a negatively charged boron atom) one of R1 further comprises a cation selected from the group consisting of protonated cations of Bronsted acids, ferrocenium cations, carbonium cations, silylium cations, and Ag +, and (when connected to a negatively charged boron atom) one of R2 also comprises a cation selected from the group consisting of protonated acid cations Bronsted, ferrocenium cations, carbonium cations, silylium cations and Ag +; and an Arf1 group and an Arf2 group together form an aromatic group substituted with fluoro, divalent of 6 to 20 carbons. Specific examples of the above salt compounds are: wherein, R is a C1-40 hydrocarbyl linking group, and L + is a cation of a Bronsted acid, or a cation of ferrocenium, carbonium, silylium or Ag +. Very preferably, L + is an ammonium cation of the formula HN + R3, wherein R is C1-50 hydrocarbyl. Most preferably, one or two R groups are C 14-50 aliphatic groups, and the remaining R group (s) is (are) C 1-4 aliphatic. Those skilled in the art will appreciate that after activation of a metal complex to a catalytically active state by the compounds herein, to the extent that a cationic derivative thereof is formed, the above separate charge compounds may include in the same the cationic derivative of said metal complex of the previous Bronsted acid, ferrocenium, carbonium, silyl or Ag + cations. For the preferred complexes, the metal is selected from Groups 3-10 of the Periodic Table of the Elements, most preferably from Group 4. Accordingly, said cationic derivative could be a cation containing a Group 3-10 metal, very preferably a cation containing a Group 4 metal. In general, the solubility of the compounds of the invention in aliphatic compounds is increased through the incorporation of one or more oleophilic groups such as long chain alkyl groups; long chain alkenyl groups; or halogen-, alkoxy-, amino-, silyl-, or germyl-substituted long chain alkyl groups or long chain alkenyl groups in the cation, L +. By the term "long chain" is meant groups having from 10 to 50 atoms that are not hydrogen in said group, preferably in a non-branched form. It is understood that the compound may comprise a mixture of oleophilic groups of different lengths in the cation. For example, a suitable compound comprises the protonated ammonium salt of the commercially available long chain amine comprising a mixture of two C14, C16 or C18 alkyl groups and a methyl group. Said amines are commercially available from Witco Corp., under the tradename Kemamine ™ T9701, and at Akzo-Nobel under the trade name Armeen ™ M2HT. Catalysts suitable for use in combination with the above cocatalysts include any compound or complex of a metal of Groups 3-10 of the Periodic Table of the Elements, capable of being activated to polymerize ethylenically unsaturated compounds through the activators of the present . Examples include diimine derivatives of Group 10 corresponding to the formula: M * is Ni (ll) or Pd (ll); K is halogen, hydrocarbyl or hydrocarbyloxy; Ar * is an aryl group, especially a 2,6-diisopropylphenyl or aniline group; CT-CT is 1, 2-ethanediyl, 2,3-butanediyl, or form a fused ring system, wherein the two T groups together are a 1,8-naphthanediyl group; and A "is the anionic component of the above separate charge activators.Catalysts similar to the above are described by M. Brookhart, et al., in J. Am. Chem. Soc, 118, 267-268 (1996) and L_ Am. Chem. Soc, 117, 6414-6415 (1995), as being polymerization active catalysts especially for the polymerization of colephins, either alone or in combination with polar comonomers such as vinyl chloride, alkyl acrylates and alkyl methacrylates. The additional catalysts include derivatives of Group 3, 4 or lanthanide metals, which are in the formal oxidation state +2, +3, or + 4. Preferred compounds include metal complexes containing from 1 to 3 bound anionic ligand groups. apo-neutral, which may be apionic, delocalized, cyclic or noncyclic linked anionic ligand groups Examples of such apionic anionic ligand groups ap are dienyl groups, allyl groups, boratabenzene groups, and arene groups, conjugated or non-conjugated, cyclic or non-cyclic. By the term "attached to p" is meant that the ligand group is attached to the transition metal by sharing electrons from a partially delocalized p-junction. Each atom in the group ap independently delocalized can be substituted with a radical selected from the group consisting of hydrogen, halogen, hydrocarbyl, halohydrocarbyl, substituted hydrocarbyl metalloid radicals, wherein the metalloid is selected from Group 14 of the Periodic Table of the Elements and said hydrocarbyl or substituted hydrocarbyl metalloid radicals are further substituted with a portion containing a heterogeneous atom of Group 15 or 16. Included within the term "hydrocarbyl" are the straight, branched and cyclic C1-2 alkyl radicals, radicals C6-2o aromatics, C7 substituted alkyl aromatic radicals. 20, and substituted aryl C7.20 alkyl radicals. In addition, two or more of said radicals together can form a fused ring system, including fused ring systems, partially or fully hydrogenated, or can form a metallocycle with the metal. Suitable substituted hydrocarbyl organic metalloid radicals include mono-, di- and tri-substituted organic metalloid radicals of the Group 14 elements, wherein each of the hydrocarbyl groups contains from 1 to 20 carbon atoms. Examples of suitable substituted hydrocarbyl organic metalloid radicals include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methylethyl, triphenylgermyl and trimethylgermyl groups. Examples of portions containing a heterogeneous Group 15 or 16 atom include amine, phosphine, ether or thioether portions or their divalent derivatives, for example, amide, phosphide, ether or thioether groups attached to the transition metal or lanthanide metal, and attached to the hydrocarbyl group or the group containing a substituted hydrocarbyl metalloid.

Examples of suitable delocalised, anionic, ap-linked groups include cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl, dihydroanthracenyl, hexahydroanthracenyl, decahydroantacenyl, and boratabenzene groups, as well as their substituted hydrocarbyl CMO derivatives or C1- 10 substituted hydrocarbyls, substituted silyl. The delocalized, anionic ap linked groups are cyclopentadienyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, tetramethyl Isyl and Icyclopentadienyl, indenyl, 2,3-dimethylindenyl, fluorenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, tetrahydrofluorenyl, octahydrofluorenyl and tetrahydroindenyl. Boratabenzenes are anionic ligands that are benzene analogs that contain boron. Previously they are already known in the art and have been described by G. Herberich et al., In Organometallics, 14,1, 471-480 (1995). The preferred boratabenzenes correspond to the formula: wherein R "is selected from the group consisting of hydrocarbyl, silyl or germyl, said R" having up to 20 non-hydrogen atoms. In complexes involving divalent derivatives of said groups attached to delocalized p, one atom thereof is bound through a covalent bond or a divalent group covalently bound to another atom of the complex, thus forming a bridge system. A suitable class of catalysts are the transition metal complexes corresponding to the formula: Lp? MXmX'nX "p, or a dimer thereof wherein: Lp is a p-linked, delocalized, anionic group that is attached to M, containing up to 50 non-hydrogen atoms, optionally two Lp groups can be linked together forming a bridge structure, and optionally an Lp can be linked to X; M is a metal of Group 4 of the Periodic Table of the Elements in the formal oxidation state +2, +3, or +4; X is a divalent, optional substituent of up to 50 non-hydrogen atoms, which together with Lp forms a metallocycle with M; X 'is an optional neutral ligand having up to 20 non-hydrogen atoms; X "in each occurrence is an anionic, monovalent moiety having up to 40 non-hydrogen atoms, optionally, two X groups" can be covalently linked to form a divalent dianonic moiety having both valences attached to M, u, optionally, two X groups " they can be covalently linked to form a neutral, conjugated or unconjugated diene which is linked by pa M (whereby M is in the oxidation state + 2), or optionally additionally one or more X groups "and one or more X groups they can be joined together thus forming a portion that is both covalently linked to M and coordinated thereto via a Lewis base functionality; I is 0, 1 or 2; m is 0 or 1; n is a number from 0 to 3; p is an integer from 0 to 3; and the sum, l + m + p, is equal to the formal oxidation state of M, except when two groups X "together form a conjugated or unconjugated neutral diene that is bound by pa M, in which case the sum of l + m is equal to the formal oxidation state of M. Preferred complexes include those containing either one or two Lp groups The last complexes include those containing a bridge group linking the two Lp groups The preferred bridge groups are those corresponding to the formula (ER * 2) X, wherein E is silicon, germanium, tin or carbon, R * independently of each occurrence is hydrogen or a selected group of silyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R * having up to 30 carbon or silicon atoms, and x is from 1 to 8. Preferably, R * independently of each occurrence is methyl, ethyl, propyl, benzyl, tert-butyl, phenyl, methoxy, ethoxy or phenoxy. complexes that contain two gru pos Lp are compounds that correspond to the formula: wherein: M is titanium, zirconium or hafnium, preferably zirconium or hafnium, in the formal oxidation state +2, +3 or +4; R3 in each occurrence, independently is selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, halogen and combinations thereof, said R3 having up to 20 non-hydrogen atoms, or adjacent R3 groups together form a divalent derivative (is thus, a hydrocarbhaltyl, siladiyl or germadiyl group) thus forming a fused ring system, and X "independently of each occurrence is an anionic ligand group of up to 40 non-hydrogen atoms, or two X groups" together form an anionic ligand group divalent of up to 40 atoms that are not hydrogen or together are a conjugated diene having from 4 to 30 atoms that are not hydrogen forming a p complex with M, so M is in the formal oxidation state + 2, and R *, E and x are as previously defined. The above metal complexes are especially suitable for the preparation of polymers having stereo-regular molecular structure. In said capacity, it is preferred that the complex possess Cs symmetry or possess a stereo-rigid, chiral structure. Examples of the first type are compounds possessing different systems attached to p, delocalised, such as a cyclopentadienyl group and a fluorenyl group. Similar systems based on 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 (1988). Examples of chiral structures include complexes of bis-indenium rae. Similar systems based on Ti (IV) or Zr (IV) were described for the preparation of sotactic olefin polymers in Wild et al., J. Organomet. Chem. 232, 233-47, (1982). Exemplary bridge ligands containing two ap-linked groups are: dimethylbis (cyclopentadiphenyl) silane, dimethylbis (tetra-methylcyclopentadienyl) silane, dimethylbis (2-ethylcyclopentadien-1-yl) silane, dimethylbis (2-t-cyclopentadiene) -1 -yl) silane, 2,2-bis (tetramethyl-cyclopentadienyl) propane, dimethylbis (inden-1-yl) silane, dimethylbis- (tetrahydroinden-1-yl) silane, dimethylbis (fluoren-1-yl) silane, dimethylbis (tetrahydrofluoren-1-yl) silane, dimethyl bis (2-methyl-4-phenylinden-1-yl) silane, dimethylbis (2-methylinden-1-yl) silane, dimethyl (cyclopentadienyl) (fluoren-1) il) silane, dimethyl (cyclopentadienyl) (octahydrofluorene-1-y) silane, dimethyl (cyclopentadienyl) (tetrahydrofluoren-1-yl) -silane, (1,1,2,2-tetramethyl-1,2-bis ( cyclopentadienyl) disilane, (1,2-bis- (cyclopentadienyl) ethane, and dimethyl-8-cyclopentadienyl) -1- (fluoren-1-yl) -methane The preferred "X" groups are selected from hydride, hydrocarbyl, silyl, germyl, halohydrocarbyl groups , halosililo, if l? l idroca rbi lo and aminohidrocarbilo, or two groups X "together form a divalent derivative of a conjugated diene or any together form a conjugated diene, attached to p, neutral. The most preferred "X" groups are C 1-20 hydrocarbyl groups An additional class of metal complexes used in the present invention correspond to the preceding formula, LpγXmX'nX "p, or a dimer thereof, wherein X is a divalent substituent of up to 50 non-hydrogen atoms which together with Lp forms a metallocycle with M. Preferred divalent X substituents include groups containing up to 30 non-hydrogen atoms comprising at least one atom which is oxygen, sulfur, boron or a member of Group 14 of the Periodic Table of the Elements directly attached to the group attached to delocalized ap, and a different atom, selected from the group consisting of nitrogen, phosphorus, oxygen or sulfur which is covalently bound to M. A preferred class of said metal coordination complexes of Group 4 used according to the present invention correspond to the formula: RJ R3 wherein: M is titanium or zirconium, preferably titanium in the formal oxidation state +2, '3 or +4; R3 in each occurrence independently is selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R3 having up to 20 atoms other than hydrogen, or adjacent R3 groups together form a divalent derivative ( Each X "is a halogen, hydrocarbyl, hydrocarbyloxy or silyl group, said group having up to 20 non-hydrogen atoms, or two X groups" together, ie, a hydrocarbyl, siladiyl or germadiyl group) thus forming a fused ring system. they form a conjugated diene of C5-30 or a divalent derivative thereof; And it is -O-, -S-, -NR *, -PR * -; and Z is SiR * 2, CR * 2, S * R * 2S * R * 2, CR * 2CR * 2, CR * = CR *, CR * 2SiR * 2, or GeR * 2l where R * is as previously defined Illustrative Group 4 metal complexes that may be employed in the practice of the present invention include: cyclopentadienyl trimethyl titanium, cyclopentadienyl triethyl titanium, cyclopentadienyl triisopropyl titanium, cyclopentadienyl triphenyl titanium, cyclopentadienyl titanium 2,4-tribencyl titanium. cyclopentadienyl dimethylpentadienyl, cyclopentadienyl titanium-2,4-dimethylpentadienyl D-triethyl phosphine, cyclopentadienyl-titanium-2,4-dimethylpentadienyl D-trimethyl phosphine, cyclopentadienyl titanium dimethyl methoxide, cyclopentadienyl titanium dimethyl chloride, pentamethylcyclopentadienyl trimethyl titanium, Indenyl trimethyl titanium, indenyl triethyl titanium, triphenyl indenyl titanium, triphenyl indenyl titanium, tetrahydroindenyl tribenzyl titanium, pentamethylcyclopentadienyl triisopropyl titanium, pentamethylcyclopene tribenzyl titanium entadienyl, titanium dimethyl methoxide of pentamethylcyclopentadienyl; pentamethylcyclopentadienyl titanium dimethyl chloride; titanium bis (? 5-2.4-dimetilpentad i enyl) titanium bis (? 5-2.4-dimetilpentadienílico) G trimetílica phosphine, titanium bis (? 5-2.4-dimetilpentadienílico) D trietílica phosphine, trimethyl titanium octahydrofluorenyl, tetrahydroindenyl titanium trimethyl, trimellitic tetrahydrofluorenyl titanium, titanium dimethyl (tert-butylamido) (1, 1 -dimethyl-2,3,4,9,10 -? - 1, 4, ,6,7,8-hexahydronaphthalenyl) dimethylsilane, dimethyl titanium (tert-butylamido) (1,1, 2,3-tetramethyl-2,3,4,9, -? - 1,4,5,6,7,8-hexahydronaphthalenyl) dimethylsilane, dibenzyl titanium of (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) -dimethyl silane, dimethyl (tert-butylamido) titanium (tetramethyl) -? 5-cyclopentadienyl) -dimethylsilane, dimethyl (tert-butylamido) titanium (tetramethyl-? 5-cyclopentadienyl) -1,2-ethanediyl, dimethyl (tert-butylamido) titanium (tetramethyl-? 5-indenyl) -dimethylsilane , titanium (III) 2- (dimethylamino) benzyl ester of (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane; titanium (III) allyl (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) -dimethylsilane, titanium (III) 2,4-dimethylpentadienyl (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, titanium (II) ) 1,4-d-1-butynyl-3-butadienyl (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, titanium (II) 1,3-pentadienyl (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) ) dimethylsilane titanium (II) 1, -diF eni I- 1, 3-butadienílico of (tert-butylamido) - (2-methylindenyl) dimet¡lsilano, titanium (II) 2,4-hexadienílico of (tert-butylamido) (2-methylindenyl) -dimethylsilane titanium (IV) 2, 3-dimethyl-1, 3-butadienílico of (tert-butylamido) - (2-methylindenyl) dimethylsilane titanium (IV) isoprenílico of (tert-butylamido) (2 -metilindenil) -dimethylsilane titanium (IV) 1, 3-butadienílico of (tert-butylamido) (2-methylindenyl) -dimethylsilane titanium (IV) 2,3-dimethyl-1, 3-butadienílico of (tert-butylamido) - (2,3-dimethylindenyl) dimethylsilane, titanium (IV) isoprenyl (tert-butylamide) gone) (2,3-dimethylindenyl) -dimethylsilane, titanium (IV) dimethyl (tert-butylamido) (2), 3-dimethylindenyl) -dimethylsilane, titanium (IV) dibenzyl (tert-butylamido) (2,3-dimethylindenyl) -dimethylsilane, titanium (IV) 1,3-butadienyl (tert-butylamido) (2,3-dimethylindenyl) ) -dimethylsilane, titanium (II) 1, 3-pentadienyl of (tert-butylamido) (2,3-dimethylindenyl) -dimethylsilane, titanium (II) 1,4-diphenyl-1,3-butadienyl (tert-butylamide) ) - (2,3-dimethylindenyl) dimethylsilane, titanium (II) 1, 3-pentadienyl (tert-butylamido) (2-methylindenyl) -dimethylsilane, titanium (IV) dimethyl (tert-butylamido) (2-) methylindenyl) dimethylsilane, titanium (IV) dibenzyl (tert-butylamido) (2-methylindenyl) -dimethylsilane, titanium (II) 1,4-diphenyl-1,3-butadienyl ester of (tert-butylamido) - (2-methyl) 4-phenylindenyl) dimethylsilane, titanium (II) 1,3-pentadienyl (tert-butylamido) - (2-methyl-4-phenylindenyl) dimethylsilane, titanium (II) 2,4-hexadienyl (tert-butylamido) - (2-methyl-4-phenylindenyl) dimethylsilane, titanium (IV) 1,3-butadienyl (tert-butylamido) (tetramethyl-? 5"cyclone) opentadienyl) dimethylsilane, titanium (IV) 2,3-dimethyl-1,3-butadienyl (tert-butylamido) - (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, titanium (IV) isoprenyl (tert-butylamido) (tetramethyl) 5-cyclopentadienyl) dimethylsilane, titanium (II) 1,4-dibenzyl-1,3-butadienyl (tert-butylamido) - (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, titanium (II) 2,4-hexadienyl of (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, titanium (II) 3-methyl-1,3-pentadienyl (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, dimethyl titanium of (ter) -butylamido) (2,4-dimethylpentadien-3-yl) -dimethylsilane, dimethyl titanium of (tert-butylamido) (6,6-dimethylcyclohexadienyl) -dimethylsilane, dimethyl titanium of (tert-butylamido) (1,1-dimethyl- 2, 3.4.9, 10 -? - 1, 4.5, 6,7,8-hexahydronaphthalen-4-yl) d -methylsilane, dimethyl titanium of (tert-butylamido) (1,1, 2,3-tetramethyl-2,3,4, 9,10 -? - 1,4,5,6,7,8-hexahydronaphthalen-4-yl) dimethylsilane, dimethyl (tert-butylamido) titanium (IV) (tetramethyl-? 5-cyclopentadienyl) methylphenylsilane, titanium (II ) 1, 4-diphenyl-1,3-butadienyl (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) methylphenylsilane, dimethyl (IV) titanium of 1 - (tert-butylamido) -2- (tetramethyl-? 5) -cyclopentadienyl) ethanediyl, and titanium (II) 1,4-d ifen-1, 3-butadienyl of 1 - (tert-butylamido) -2- (tetramethyl-? 5-cyclopentadienyl) ethanediyl. Complexes containing two Lp groups, including bridge complexes suitable for use in the present invention, include bis (cyclopentadienyl) dimethyl zirconium, bis (cyclopentadienyl) dibenzyl zirconia, bis (cyclopentadienyl) methyl benzyl zirconium, zirconium methyl phenyl of bis (cyclopentadienyl), bis (cyclopentadienyl) diphenylic zirconia, bis (cyclopentadienyl) allyl titanium, bis (cyclopentadienyl) zirconium methoxide, bis (cyclopentadienyl) zirconium methyl chloride, bis (pentamethylcyclopentadienyl) dimethyl zirconium, bis (pentamethylcyclopentadienyl) dimethyl titanium, bis (indenyl) dimethyl zirconium, indenyl fluorenyl dimethyl zirconium, methyl (2- (dimethylamino) benzyl zirconium) bis (indenyl) zirconium, bis (indenyl) methyltrimethylsilyl zirconium, bis (methyltrimethylsilyl zirconium) tetrahydroindenyl), bis (pentamethylcyclopentadienyl) methylbenzyl zirconium, dibenzyl zirconium of bis (pentamethylcyclopentadienyl), bis (pentamethylcyclopentadienyl) zirconium methyl methoxide, bis (pentamethylcyclopentadienyl) zirconium methyl ester, bis (methylethylcyclopentadienyl) dimethyl zirconium, bis (butylcyclopentadienyl) dibenzyl zirconia, bis (t-butylcyclopentadienyl) dimethyl zirconium ), bis (ethyltetramethylcyclopentadienyl) dimethyl zirconium, bis (methylpropylcyclopentadienyl) dibenzyl zirconia, bis (trimethylsilylcyclopentadienyl) zirconium dimethylsilyl-bis (cyclopentadienyl) zirconium, dimethylsilyl-bis (tetramethylcyclopentadienyl) allyl titanium (III), dichloride of dimethylsilyl-bis (t-butylcyclopentadienyl) zirconium, dimethylsilyl-bis (n-butylcyclopentadienyl) zirconium dichloride, titanium (III) 2- (dimethylamino) benzyl (methylene-bis- (tetramethylcyclopentadienyl), titanium (III) 2 - (Methylene-bis- (n-butylcyclopentadienyl) benzylic (dimethylamino), zircon benzyl chloride io of dimethylsilyl-bis (indenyl), dimethylsilyl-bis (2-methylindenyl) dimethyl zirconium, dimethylsilyl-bis (2-methyl-4-phenylindenyl) zirconium, zirconium-1,4-diphenyl-1,3-butadienyl zirconium of d imeti Isil i l-bis- (2-methylindenyl), zirconium (II) 1,4-dif e, or I-1,3-butadienyl dimethylsilyl-bis- (2-methyl-4-phenylindenyl), zirconium ( II) 1, 4-d if eni I-1,3-dimethylsilyl-bis- (tetrahydroindenyl) butadiene, dimethylsilyl-bis (fluorenyl) zirconium methyl chloride, bis (trimethylsilyl) zirconium dimethylsilyl-bis (tetrahydrofluorenyl), dibenzyl zirconium (isopropylidene) (cyclopentadienyl) (fluorenyl), and dimethylsilyl (tetramethylcyclopentadienyl) - (fluorenyl) dimethyl zirconium. Other catalysts, especially catalysts containing Group 4 metals, will, of course, be apparent to those skilled in the art. The cocatalysts of the invention can also be used in combination with an oligomeric or polymeric alumoxane compound, a tri (hydrocarbyl) aluminum compound, a di (hydrocarbyl) (hydrocarbyloxy) aluminum compound, a di (hydrocarbyl) (dihydrocarbyl-amido) compound aluminum, a bis (di-hydrocarbyl-amido) (hydrocarbyl) aluminum compound, a di (hydrocarbyl) amido (disilyl) aluminum compound, a di (hydrocarbyl) -amido (hydrocarbyl) (silyl) aluminum compound, a bis (dihydrocarbylamido) compound ) (silyl) aluminum, or a mixture of the above compounds, having from 1 to 20 non-hydrogen atoms in each hydrocarbyl group, hydrocarbyloxy or silyl, if desired. These aluminum compounds are usefully used for their beneficial ability to sweep impurities such as oxygen, water and aldehydes from the polymerization mixture. Preferred aluminum compounds include C2-6 aluminum trialkyl compounds, especially those wherein the alkyl groups are ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl or isopentyl, dialkyl (aryloxy) aluminum compounds containing 1-6 carbons in the alkyl group and from 6 to 18 carbons in the aryl group (especially (3,5-di (t-butyl) -4-methylphenoxy) diisobutylaluminum), methylalumoxane, modified methylalumoxane and diisobutylalumoxane. The molar ratio of the aluminum compound to the metal complex preferably is from 1: 10,000 to 1000: 1, preferably from 1: 5000 to 100: 1, most preferably from 1: 100 to 100: 1. The molar ratio of catalyst / cocatalyst employed preferably varies from 1:10 to 10: 1, preferably from 2.1: 1 to 1: 1.5 and most preferably from 2.05: 1 to 1: 1. If desired, mixtures of the activating cocatalysts of the present invention may also be employed. Suitable polymerizable addition monomers include ethylenically unsaturated monomers, acetylenic compounds, conjugated and non-conjugated dienes, and polyenes. Preferred monomers include olefins, for example, alpha-olefins having from 2 to 20,000, preferably from 2 to 20, most preferably from 2 to 8 carbon atoms, and combinations of two or more of said alpha-olefins. Particularly suitable alpha-olefins include, for example, ethylene, propylene, 1-butene, 1-pentene, 4-methylpentene-1, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1 -undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene or combinations thereof, as well as oligomeric or polymeric reaction products terminated in long chain vinyl formed during the polymerization, and α-olefins of C10- 30 specifically added to the reaction mixture in order to produce relatively long chain branches in the resulting polymers. Preferably, the alpha-olefins are ethylene, propene, 1-butene, 4-methyl-pentene-1, 1-hexene, 1-octene and combinations of ethylene and / or propene with one or more other alpha-olefins. Other preferred monomers include styrene, halogen or substituted alkyl styrene, tetrafluoroethylene, vinylcyclobutene, 1,4-hexadiene, dicyclopentadiene, ethylidene norbornene and 1,7-octadiene, mixtures of the aforementioned monomers can also be used. In general, polymerization can be achieved at conditions well known in the art for polymerization reactions of the Ziegler-Natta or Kaminsky-Sinn type. If desired, suspension, solution, slurry, gas phase or high pressure can be used, if it is used intermittently or continuously or other process conditions. Examples of such well-known polymerization processes are described in WO 88/02009, patents of E.U.A. Us. ,084,534, 5,405,922, 4,588,790, 5,032,652, 4,543,399, 4,564,647, 4,522,987, etc. The preferred polymerization temperatures are 0-250 ° C. The preferred polymerization pressures are atmospheric at 3000 atmospheres. Preferred processing conditions include solution polymerization, most preferably continuous solution polymerization processes, conducted in the presence of an aliphatic or cyclic liquid diluent. By the term "continuous polymerization" it is meant that at least the products of the polymerization are continuously removed from the reaction mixture, such as, for example, by the devolatilization of a portion of the reaction mixture. Preferably, one or more reagents are also continuously added to the polymerization mixture during the polymerization. Examples of suitable aliphatic or alicyclic diluents include straight and branched chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; and perfluorinated hydrocarbons such as perfluorinated C4.10 alkanes. Suitable diluents also include aromatic hydrocarbons (particularly for use with aromatic α-olefins such as styrene or ring-substituted alkyl styrenes) including toluene, ethylbenzene or xylene, as well as liquid olefins (which may act as monomers or comonomers) including ethylene, propylene, butadiene, cyclopentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1,4-hexadiene, 1-octene, 1-decene, styrene, divinylbenzene, allylbenzene and vinyltoluene (including all the isomers alone or in combination). Mixtures of the above are also suitable. In most polymerization reactions, the molar ratio of catalyst: polymerizable compounds employed is 10"12: 1 to 10" 1: 1, most preferably 10"12: 1 to 10" 5: 1. The catalyst composition of the invention can also be used in combination with at least one homogeneous or heterogeneous polymerization catalyst in separate reactors connected in series or in parallel to prepare polymer blends having desirable properties. An example of said process is described in WO 94/00500, equivalent to the application of E.U.A. Series No. 07 / 904,770. A more specific process is described in the co-pending application of E.U.A. Series No. 08/10958, filed January 29, 1993. Molecular weight control agents can be used in combination with the cocatalysts herein. Examples of such molecular weight control agents include hydrogen, trialkylaluminum compounds or other known chain transfer agents. A particular benefit of the use of the present cocatalysts is the ability (depending on the reaction conditions) to produce narrow molecular weight a-olefin homopolymers and copolymers at greatly improved catalyst efficiencies. Preferred polymers have an Mw / Mn less than 2.5, most preferably less than 2.3. such narrow molecular weight distribution polymer products are highly desirable due to the improved tensile strength properties. The catalyst composition of the present invention can also be employed to have advantage in gas phase polymerization and olefin copolymerization. Gas phase processes for the polymerization of olefins, especially the homopolymerization and copolymerization of ethylene and propylene, and the copolymerization of ethylene with higher alpha-olefins such as, for example, 1-butene 1- are well known in the art. hexene, 4-methyl-1-pentene. These processes are used commercially on a large scale for the manufacture of high density polyethylene (HDPE), medium density polyethylene (MDPE)., linear low density polyethylene (LLDPE) and polypropylene. The gas phase process employed can be, for example, of the type employing a mechanically agitated bed or a fluidized gas bed as the polymerization reaction zone. The process is preferred in which the polymerization reaction is carried out in a vertical cylindrical polymerization reactor containing a fluidized bed of polymer particles supported above a perforated plate, the fluidization grid, through a gas flow of fluidization. The gas used to fluidize the bed comprises the monomer or monomers to be polymerized, and also serves as a heat exchange medium to remove the heat of reaction from the bed. Hot gases emerge from the upper part of the reactor, usually via a calming zone, also known as a velocity reduction zone, having a wider diameter than the fluidized bed, and where the fine particles entering the gas stream they have the opportunity to gravitate back to the bed. It can also be advantageous to use a cyclone to remove ultra-fine particles from the gas stream. The gas is then normally recirculated to the bed through a blower or compressor and one or more heat exchangers to separate the gas from the heat of the polymerization. A preferred method for cooling the bed, in addition to the cooling provided by the cold recirculating gas, is to feed a volatile liquid into the bed to provide an evaporative cooling effect. The volatile liquid used in this case can be, for example, a volatile inert liquid, for example, a saturated hydrocarbon having from 3 to 8, preferably from 4 to 6 carbon atoms. In the event that the monomer or comonomer itself is a volatile liquid, or can be condensed to provide such a liquid, it can be suitably fed into the bed to provide an evaporative cooling effect. Examples of olefin monomers which can be used in this manner include olefins containing from 3 to 8, preferably from 3 to 6, carbon atoms. The volatile liquid evaporates in the hot fluidized bed to form gas, which is mixed with the fluidizing gas. If the volatile liquid is a monomer or comonomer, it will experience some polymerization in the bed. The evaporated liquid then emerges from the reactor as part of the hot recirculation gas, and enters the compression / heat exchanger part of the recirculation loop. The recirculation gas is cooled in the heat exchanger and, if the temperature at which the gas is cooled is below the dew point, the liquid will precipitate out of the gas. This liquid is desirably recirculated continuously to the fluidized bed. It is possible to recirculate the precipitated liquid to the bed as droplets of liquid carried in the recirculation gas stream, as described, for example, in EP-A-89691, US-A-4543399, WO 94/225495 and US-A -5352749. A particularly preferred method for recirculating liquid to the bed is to separate the liquid from the recirculating gas stream and re-inject this liquid directly to the bed, preferably using a method that generates fine drops of the liquid within the bed. This type of process is described in WO 94/28032. The polymerization reaction occurring in the gas fluidized bed is catalysed through the continuous or semi-continuous addition of catalyst. Said catalyst can be supported on an inorganic or organic support material, if desired. The catalyst can also be subjected to a pre-polymerization step, for example, by polymerizing a small amount of olefin monomer in a liquid inert diluent, to provide a catalyst composite comprising catalyst particles embedded in olefin polymer particles. The polymer is produced directly in the fluidized bed through catalysed (co) polymerization of monomer (s) on the fluidized catalyst particles, supported catalyst or prepolymer inside the bed. The start of the polymerization reaction is achieved using a bed of preformed polymer particles, which, preferably, is similar to the objective polyolefin, and conditioning the bed by drying with an inert gas or nitrogen before the introduction of the catalyst, the monomer (s) and any other gases that are desired to have in the recirculation gas stream, such as a diluent gas, a hydrogen chain transfer agent, or an inert condensable gas when operating in a gas phase condensation mode . The produced polymer is discharged continuously or discontinuously from the fluidized bed as desired, optionally exposed to a catalyst annihilator and optionally pelletized. It is understood that the present invention can be operated in the absence of any component that has not been specifically described. The following examples are provided for the purpose of further illustrating the invention and are not constructed as limiting. Unless otherwise stated, all parts and percentages are expressed on a weight basis.

EXAMPLE 1 Preparation of (te transfluoro-1,4-phenylene) -bis- (di (pentafluoro phenyl) borane) ((C6F5) 2B-C6F4-B (C6F5) 2) In a thin-walled flask containing a J. Young valve , 1, 4-C6F4 (SnMe3) 2 (0.60g, 1.26 mmoles) and (C6F5) 2BCI (2.87 g, 7.56 mmoles) were added. 40 ml of toluene were added, the flask was evacuated to 0.1 torr, and the J. Young valve closed. The flask was heated at 140 ° C for 72 hours. The solvent was removed in vacuo, and the residue was washed with pentane (4x20ml). The resulting light yellow solid was exposed under dynamic vacuum (10 ~ 5 torr) for 12 hours, giving the desired product as a pale yellow microcrystalline solid (0.75 g, 71%). 19F NMR (CD2Cl2): d -125.7 (br, 8F, ortho C6F5), -128.2 (br, 4F, C6F4), -141.1 (br, 4F, for C6F5), -159.1 (br, 8F, meta C6F5) ppm . MS (El, 6.3 V): m / e 838 (M \ 100 percent).

Activation of the Metal Complex The combination of the diborane compound of Example 1 with zirconozene dimethyl zirconium of zirconocene in CD2Cl2 at 25 ° C in an atomic ratio of 1: 1 and 2: 1 (Zr: B) gave two cationic reaction products corresponding to the derivatives of the monoanionic salt (1) and the dianonic salt (2) according to the following scheme: (CdHsJaZr "* - CH3 (C5H5) 2ZrCH3 (C6H5) 2Zr + CH3 NMR data for 1: 1 H NMR (CD2Cl2): d 6.39 (s, 10H), 0.68 (s, 3H), 0.31 (br, 3H) ppm. 19F NMR (CD2CI2): d -127.5 (d, 3JFF = 21 HZ, 3F), -129.3 (t, 3JFF = 18 Hz, 1F), -131.8 (m, 1 F), -132.4 (m, 6F) , -136.7 (s, 1F :), -144.8 (s, 1F), -159.0 (br, 1F), -160.0 (m, 4F), -163.8 (br, 2F), -164.2 (t, 3JFF = 19 HZ, 3F) NMR data for 2: 1H NMR (CD2Cl2): d 6.29 (s, 20H), 0.45 (br, 6H), 0.29 (br, 6H) ppm. 19 F NMR (CD2Cl2): d -131.5 (d, 3 JFF = 18 Hz, 8F, ortho C6F5), -142.8 (br, 4F, C6F4), -162.4 (br, 4F, for C6F5), -165.3 (br, 8F, meta C6F5) ppm.

EXAMPLE 2 Preparation of (tetrafluoro-1, 2-phenylene) -bis- (di (pentaf luorophenyl) borane) A) Preparation of [1,2-C6F4BCI] 2 An excess of BCI3 (about 5.0 g, 44 mmol) was condensed in a thin-walled flask containing a J. Young valve and 1, 2-C6F4 (SnMe3) 2 (5.3 g, 11.1 mmol) at -196 ° C. The flask was evacuated to 0.05 torr, and the J. Young valve closed. The reaction mixture was heated at 180 ° C for 18 hours. Excess BCI3 was removed under dynamic vacuum, giving a beige solid, slightly moist. The product was extracted with pentane (3x20 ml), leaving behind 65% of the byproduct Me3SnCI. The remaining Me3SnCl was sublimed at 40 ° C / 10"5 torr The product was then sublimed at 90 ° C / 10 ~ 5 torr, giving [1, 2-C6F4BCI] 2 as a yellow solid (1.15 g, 53%) 19F NMR (C6D6): d -122.7 (m, 4F), -143.9 (m, 4F) ppm, 13C NMR (CDCl3): d 152.6 (d, 1JC = 262 Hz), 144.6 (d, 1JCF = 260 Hz ), 122.8 (br, BC) ppm MS (El, 8.7 V) (percentage of intensity): 392 (16), 391 (18), 390 (67), 389 (M +, 47), 388 (100) , 387 (51), 342 (21), 318 (22), 304 (28), 250 (25), 201 (30), Anal, Cale, for C12F8B2Cl2: C, 37.1; H, 0.0 Found: C, 38.2, H. 0.3.

B) Preparation of [1, 2-C6F4B (C6F5)] 2 In a thin-walled flask containing a J. Young valve, [1, 2-C6F4BCI] 2 (0.265 g, 0.68 mmol) and (C6F5) were placed. 2SnMe2 (0.33 g, 0.68 mmol). 20 ml of toluene were added, the flask was evacuated to 0.1 torr, and the J. Young valve closed. The reaction solution was heated at 140 ° C for 72 hours, giving a bright yellow solution. The solution was concentrated to 10 ml and then heated to dissolve all solids. The slow cooling of this solution at -78 ° C gave 2 pale yellow crystals. It was found that this solid contains a small amount of Me2SnCI2, which can be removed under dynamic vacuum (10"5 torr / 12 hours), giving the desired product, [1,2-C6F4B (C6F5)] 2, as a solid clear yellow crystalline (0.35 g, 68%) Alternatively, due to the sensitivity of the compound, the crude reaction solution could be exposed to dynamic vacuum (10"5 torr) for 12 hours, giving the product in a purity of> 0.05 g. 95%, without the need for crystallization. 19 F NMR (dß-toluene): d -118.2 (br, 4F, ortho C6F4), -133.9 (dd, 3JFF = 25.1 Hz, 4JFF = 7.9 Hz, 4F, ortho C6F5), -138.9 (m, 4F, meta C6F4 ), -152.1 (t, 3JFF = 21 Hz, 2F, for C6F5), -161.4 (ddd, 3JFF = 22 Hz, 3JFF = 22 Hz, 5JFF = 7 Hz, 4F, goal C6F5) ppm. 3C NMR (CDCl 3): d 156.1 (d, JCF = 267 Hz), 145.9 (d, 1JCF = 265 Hz), 144.3 (d, 1JCF = 241 HZ), 141.6 (d, 1JCF = 265 HZ), 137.6 (d , 1JCF = 253 Hz), 128.3 (br), 123.7 (br) ppm.

Crystal Data C24F18B2 »(2C7H8); space group, monoclinic P2! / c; a = 22,836 (4), b = 10,846 (3), c = 13,767 (3) A; b = 99.66 (2) °; V = 3361 (1) A; b = 99.66 (2) °; V = 3361 (1) A3; Z = 4; dcaic = 1652 g / cm3; at -120 ° C. The structure was solved through direct methods. Regarding the scarcity of data, the fluorine atoms were anisotropically refined and the remaining non-hydrogen atoms were refined isotropically. The hydrogen atoms were included in "idealized" positions and were not retined. The final cycle of the refinement of last squares of complete matrix was based on 2042 observed reflections (l> 3.00s (l)) and 324 variable parameters and converged (longer parameter displacement was 0.12 times its esd) with factors of sub-heavy and heavy agreements of R = 0.051 and Rw = 0.039. For clarity of crystallographic discussion, it should be noted that there are two middle molecules in the asymmetric unit, and consequently there are two independent joining distances and angles for each junction / angle of 2.

Activation of Metal Complexes The combination of the diborane compound of Example 2 with the zirconium dimethyl of zirconocene bisciclopentadienyl in CD2CI2 at 25 ° C in an atomic ratio of 1: 1 and 2: 1 (Zr: B) of two reaction products cationic that correspond to the derivatives of the monoanionic salt (3) and the dianonic salt (4) according to the following scheme: NMR data for 3: 19F (CD2CI2, 25 ° C): d -123.1 (br, 2F), -132.4 (M, 3F), -134.0 (br, 2F), -134.8 (br, IF), -145.0 (br, 2F), -155.4 (t, 3JFF = 21 Hz, IF), -158.9 (m, 2F), -160.0 (M, 1F), -161.8 (br, 1F), -162.5 (br, 1F) , -164.1 (br, t, 3JFF = 21 Hz, 2F) ppm. 1H (CD2Cl2, 25 ° C): d 6.34 (s, 10H), 0.66 (s, 3H), 0.17 (br, 3H) ppm.

NMR data for 4: 19F (CD2Cl2, 25 ° C): d -132.7 (br, 2F, ortho C6F5), -134.7 (br, 4F, ortho C6F4), -136.4 (br, 2F, ortho C6F5), - 161.6 (t, 3JFF = 20 Hz, 2F, stop C6F5), -162.6 (d, 3JFF = 19 Hz, 4F, goal C6F4), -164.4 (br, 2F, goal C6F5), -165.4 (br, 2F, goal C6F5) ppm. H (CD2Cl2, 25 ° C): O 6.22 (s, 10H), 0.69 (s, 3H), 0.19 (br, 3H) ppm; a slight excess of (C5H5) 2ZrMe2 was present in this example, and resonances attributable to this compound were also present.

Polymerizations A stirred two-liter reactor was charged with 640 ml of the Isopar ™ solvent, and 150 g of propylene. Hydrogen (25 ml at 0.2? MPa) was added as a molecular weight control agent. The reactor was heated to 70 ° C. the catalyst composition was prepared in a drying box by mixing together 0.005M of toluene solutions of the titanium dimethyl (t-butylamido) dimethyl (5-tetramethylcyclopentadienyl) catalyst, and the compounds of Examples 1 or 2 to give atomic ratios of B / T¡ of 1: 1 or 2: 1. After a mixing time of 5 minutes, the solutions were then transferred to an addition loop and injected into the reactor. The polymerization was allowed to process for 10 minutes, while maintaining the reaction temperature at 70 ° C. The polymer solution was transferred from the reactor to a glass vessel and dried in a vacuum oven for 16 hours at a maximum temperature of 120 ° C. The results are contained in Table 1.

TABLE 1 Operation μmoles of Cocatalyst Time of Grams of Efficiency (Kg of catalyst (μmoles) reaction, minutes Polymer polymer / g of Tí) 1 * 6 FAB1 (6) 10 29.7 103 2 0.75 Ej.2 (0.75) 10 70.9 1.974 3 * 6 FAB1 (6) 10 37.0 129 4 1.5 Ex.2 (0.75) 10 66.4 925 3 Ex.1 (3) 18.5 29.7 207 6 6 Ex.1 (3) 10 49.2 171 * not an example of the invention 1 tris (pentafluorophenyl) borane

Claims (9)

1. - A compound that corresponds to the formula: wherein: R1 and R2 independently of each occurrence are C1-2o hydrocarbyl groups, halohydrocarbyl or halocarbyl, and optionally and additionally comprising a cation portion, and Arf1-Arf2 in combination, independently of each occurrence, is an aromatic group substituted with Fluoro, divalent of 6 to 20 carbons.

2. The compound according to claim 1 corresponding to the formula:

3. - The compound according to claim 1 corresponding to the formula: wherein: R1 and R2 independently of each occurrence are C1-2o hydrocarbyl groups. halohydrocarbyl or halocarbyl, and (when connected to a negatively charged boron atom) one of R1 further comprises a cation selected from the group consisting of protonated cations of Bronsted acids, ferrocenium cations, carbonium cations, silylium cations, and Ag +, and cationic derivatives of a metal complex of Group 3-10 and (when connected to a negatively charged boron atom) one of R2 further comprises a cation selected from the group consisting of protonated cations of Bronsted acids, ferrocenium cations , carbonium cations, silylium and Ag + cations, and cationic derivatives of a metal complex of Group 3-10; and a group Arf1 and a group Arf2 together form a divalent bridge group of C6-2o-

4. A compound according to claim 3 corresponding to the formula: wherein, L + is a cation of a Bronsted acid, or a cation of ferrocenium, carbonium, silylium or Ag +.

5. A catalyst system for the polymerization of α-olefins comprising, in combination, a metal complex of the Group 4 and a compound according to any of claims 1-4, or its reaction product.

6. A polymerization process comprising contacting one or more α-olefins under polymerization conditions with a catalyst system according to claim 5.

7. A process according to claim 6, which is a solution polymerization.

8. A polymerization process according to claim 7, which is a continuous solution polymerization.

9. - A polymerization process according to claim 6, which is a gas phase polymerization.