ES2188235T3

Bridged metal complexes for gas phase polymerizations

Abstract

An olefin polymerization process comprising contacting one or more olefin monomers under gas phase polymerization conditions with a catalyst composition comprising a metal complex corresponding to the following formulas: ** (Formula) ** in the that: M is titanium, zirconium, or hafnium in the oxidation state +4, +3 or +2; Y1 and Y2 are independently an anionic, cyclic or non-cyclic 7-linked group, NR1, PR1; NR12 or PR12; Z is boron or aluminum; Q is a neutral, anionic or dianionic ligand group depending on the oxidation state of M; j is 1, 2 or 3 depending on the oxidation state of M and the electronic nature of Q; T, independently in each case, is: ** (Formula) ** R1 is, independently in each case, hydrogen, a hydrocarbyl group, a tri (hydrocarbyl) silyl group, or a tri (hydrocarbyl) silylhydrocarbyl group, said groups containing R1 up to 20 atoms without counting the hydrogens; R5 is R1 or N (R1) 2; and two groups R1 together or one or more groups R1 together with R5 can optionally join to form a ring structure.

ES2188235T3, drawing sheet 1 — Sheet 1 of 19

Term

Term ended

Projected expiry passed 8 September 2019, 7 years ago.

15 claims: 3 independent, 12 dependent

1
ES 2 188 235 T3 REIVINDICACIONES 1. Un proceso de polimerizacioán de olefinas que comprende poner en contacto uno o máas monoámero de olefina en condiciones de polimerizaciáon en fase gaseosa con una composicioán de catalizador que comprende un complejo metáalico que corresponde a las siguientes foármulas:PR en las que: M es titanio, circonio, o hafnio en el estado de oxidacioán +4, +3 o +2;Y 1 eY 2 * son independientemente un grupo π-unido amámco, cíclico o no cíclico, NR 1 2;PR 1 ;NR 1 2 o Z es boro o aluminio;Q es un grupo ligando neutro, anioánico o dianioánico dependiendo del estado de oxidaciáon de M;j es 1, 2 o 3 dependiendo del estado de oxidaciáon de M y de la naturaleza electroánica de Q;T, independientemente en cada caso, es: R 1 es, independientemente en cada caso, hidroágeno, un grupo hidrocarbilo, un grupo tri(hidrocarbil)sililo, o un grupo tri(hidrocarbil)sililhidrocarbilo, conteniendo dichos grupos R 1 hasta 20 áatomos sin contar los hidroágenos;R 5 es R 1 o N(R 1 )2;y dos grupos R 1 juntosounoomaás grupos R 1 junto con R 5 pueden unirse opcionalmente para formar una estructura de anillo.
2
El proceso de la reivindicaciáon 1, en el que el complejo metaálico correspondiente a la fáormula 1 se representa por la fáormula 4, 5, 6, 7, 8 o 9. ES 2 188 235 T3 en las que M, Z, T, R 1 , Q y j son como se han definido en la reivindicaciáon 1;R 2 es hidráogeno, o un grupo hidrocarbilo, halohidrocarbilo, dihidrocarbilaminohidrocarbilo, tri(hidrocarbilsilil)hidrocarbilo, Si(R 3 )3, N(R 3 )2 ,oOR 3 de hasta 20 áatomos de carbono o silicio, y opcionalmente pueden unirse entre sá dos grupos R 2 adyacentes formando de esta manera una estructura de anillo condensado, especialmente un ligando de indenilo o un ligando de indenilo sustituido;y R 3 es independientemente hidráogeno, un grupo hidrocarbilo, un grupo trihidrocarbilsililo o un grupo trihidrocarbilsililhidrocarbilo, teniendo dicho R 3 hasta 20 áatomos sin contar los hidroágenos.
3
Un proceso de acuerdo con la reivindicacioán 2, en el que M estaá en el estado de oxidaciáon +4, j = 2 y Q, independientemente en cada caso, es haluro, hidruro, hidrocarbilo, sililhidrocarbilo, oáxido de hidrocarbilo, o dihidrocarbilamida, teniendo dicho Q hasta 20 aátomos sin contar los hidráogenos, o dos grupos Q conjuntamente forman un grupo alcanodiilo o un ligando de dieno C4-40 conjugado que junto con M forma un metalociclopenteno.
4
Un proceso de acuerdo con la reivindicacioán 2, en el que M estaá en el estado de oxidaciáon +3, j = 1 y Q es 1) un ligando de estabilizaciáon anioánico monovalente seleccionado entre el grupo compuesto por grupos alquilo, cicloalquilo, arilo, sililo, amido, fosfido, alcoxi, ariloxi, sulfido y mezclas de los mismos, estando dicho Q adicionalmente sustituido con una amina, fosfina, áeter o tioáeter que contiene un sustituyente capaz de formar un enlace covalente coordinado o un enlace quelante con M, teniendo dicho ligando hasta 50 aátomos sin contar los hidráogenos;o 2) un grupo hidrocarbilo C3-10 que comprende una insaturacioán etiláenica capaz de formar un enlace η 3 con M.
5
Un proceso de acuerdo con la reivindicaciáon 2, en el que M estaá en el estado de oxidaciáon +2, j = 1 y Q es un dieno conjugado neutro, opcionalmente sustituido con uno o maás grupos tri(hidrocarbil)sililo o tri(hidrocarbilsilil)hidrocarbilo, teniendo dicho Q hasta 40 áatomos de carbono y formando un complejo π con M. 6
6
Un proceso de acuerdo con la reivindicacioán 3, en el que el complejo metáalico corresponde a la Fáormula 4a, 5a, 6a, 7a, 8a o 9a, donde las definiciones de M, Z, R 1 ,R 2 yR 3 son como se han definido en la reivindicaciáon 3:ES 2 188 235 T3 R 2 R 2 /¾ R’sN-Z R 2 . y” 02 NPf / \ pjN—Ζ^^ΜΟζ r1 2 N ” \ / \tf/ Fórmula 4a Fórmula Sa Fórmula 6a R’^-2 rá-z tf MQ2 R 2 R’jN-Z^NRf R 2 Fórmula 7a Fórmula 6a f0 R'zN 1 ,-Nfl 3 r\n-z \ r 1 / 4 ° 2 R 2^ ^^*|4Ry Formulada y Q, independientemente en cada caso, es un grupo haluro, hidrocarbilo, hidrocarbiloxi o dihidrocarbilamida de hasta 10 aótomos sin contar los hidroógenos, o dos grupos Q conjuntamente forman un ligando de dieno C4-20 que junto con M forma un metalociclopenteno.
7
Un proceso de acuerdo con la reivindicacióon 4, en el que el complejo metaólico corresponde a la Fóormula 4b, 5b, 6b, 7b, 8b o 9b, donde las definiciones de M, Z, R 1 ,R 2 yR 3 son como se han definido en la reivindicacióon 4:y Q, en cada caso, es un ligando de estabilizacioón anioónico monovalente seleccionado entre el grupo compuesto por grupos alquilo, cicloalquilo, arilo y sililo, estando dicho grupo sustituido adicionalmente con ES 2 188 235 T3 unoomóas sustituyentes amina, fosfina o óeter capaces de formar un enlace covalente coordinado o un enlace quelante con M, y teniendo dicho Q hasta 30 aótomos distintos de hidroógeno;o Q es un grupo hidrocarbilo C3-10 que comprende una insaturacióon etilóenica capaz de formar un enlace η 3 con M.
8
Un proceso de acuerdo con la reivindicacióon 5, en el que el complejo metóalico corresponde a la Foórmula 4c, 5c, 6c, 7c, 8c o 9c, donde las definiciones de M, Z, R 1 ,R 2 yR 3 son como se han definido en la reivindicacióon 5:y Q, en cada caso, es un dieno conjugado neutro, opcionalmente sustituido con uno o maós grupos tri(hidrocarbil)sililo o tri(hidrocarbil)sililhidrocarbilo, teniendo dicho Q hasta 30 aótomos sin contar los hidróogenos y formando un complejo π con M.
9
Un proceso de acuerdo con cualquiera de las reivindicaciones 1-8, en el que M es circonio o hafnio.
10
Un proceso de acuerdo con la reivindicacióon 9, en el que Z es boro.
11
Un proceso de acuerdo con la reivindicacioón 1, en el que el complejo metóalico es dicloruro de dimetilamidoboraño-bis(η 5 -ciclopeñtadieñil)circoñio, dicloruro de dimetilamidoborañobis(η 5 -iñdeñ-1il)circomo, dicloruro de dimetilamidoboraño-bis(η 5 -2-metil-4-femlmdeñ-1-il)circomo, dicloruro de dimetilamidoboraño-bis(η 5 -2-etil-4-feñiliñdeñ- 1-il)circomo, dicloruro de dimetilamidoboraño-bis-©^^sopTOpil-4-feñiliñdeñ-1-il)circoñio, dicloruro de dimetilamidoboraño-bis(η 5 -2-metil-4-bis(3,5-trifluorometil)feñiliñdeñ-1-il)circoñio, dicloruro de dimetilamidobor ño-bis(η 5 -3-t-butiliñdeñ-1-il)circoñio, dicloruro de diisopropilamidoboraño-bis(η 5 -ciclopeñtadieñil)circoñio, dicloruro de diispropilamidoborañobis(η 5 -iñdeñ- 1-il)circomo, dicloruro de diisopropilamidoboraño-bis(η 5 -2-metil-4-feñiliñdeñ- 1-il)circonio, dicloruro de diisopropilamidoboraño-bis(η 5 -2-et l-4-femlmdeñ-1-il)circomo, dicloruro de diisopropilamidoboraño-bis(η 5 -2-isopropil-4-feñiliñideñ- 1-il)circomo, dicloruro de diisopropilamidoboraño-bis(η 5 -2metil-4-bis(3,5-trifluorometil)feñiliñdeñ-1-il)circoñio, dicloruro de diisopropilamidoboraño-bis(η 5 -3-t-butilinden-1-il)circonio;dicloruro de difemlamidoborañobis(η 5 -ciclopeñtadieml)circomo, dicloruro de difeñilamidoborañobis(η 5 -iñdeñ-1-il)circoñio, dicloruro de difemlamidoboraño-bis(η 5 -2-metil-4-femlmdeñ-1-il)circomo, dicloruro de difeñilamidoboraño-bis(η 5 -2-etil-4-feñiliñdeñ 1-il)circomo, dicloruro de difeñilamidoborañobis(η 5 -2-isopropil-4-feñiliñdeñ-1-il)circoñio, dicloruro de difeñilamidoboraño-bis(η 5 -2-metil-4-bis(3,5-trifluorometil)feñiliñdeñ-1-il)circoñio, dicloruro de difemlamidoboraño-bis(η 5 -3-t-butilmdeñ-1-il)circomo, ES 2 188 235 T3 dimetilamidoborano-bis(r 5 -ciclopentadienil)circonio 1,4-difenil-1,3-butadieno, dimetilamidoboranobis(r 5 -inden-1-il)circonio 1,4-difenil-1,3-butadieno, dimetilamidoborano-bis(r 5 -2-metil-4-fenilinden-1-il)circonio 1,4-difenil-1,3-butadieno, dimetilamidoborano-bis(r 5 -2-etil-4-fenilinden-1-il)circonio 1,4-difenil-1,3-butadieno, dimetilamidoborano-bis(r 5 -2-isopropil-4-fenilinden-1-il)circonio 1,4-difenil-1,3-butadieno, d metilamidoborano-bis(r 5 -2-metil-4-bis(3,5trifluorometil)fenilinden-1-il)circonio 1,4-difenil-1,3-butadieno, dimetilamidoborano-bis(r 5 -3-t-butilinden-1-il)circonio 1,4-difenil-1,3-butadieno, diisopropilamidoborano-bis(r 5 -ciclopentadienil)circonio 1,4-difenil-1,3-butadieno, diisopropilamidoboranobis(r 5 -inden-1-il)circonio 1,4-difenil-1,3-butadieno, diisopropilamidoborano-bis(r 5 -2-metil-4-fenilinden-1-il)circonio 1,4-difenil-1,3-butadieno, diisopropilamidoborano-bis(r 5 -2-etil-4-fenilinden-1-il)circonio 1,4-difenil-1,3-butadieno, diisoprop lamidoborano-bis(r 5 -2-isopropil-4-fenilinden-1-il)circonio 1,4difenil-1,3-butadieno, diisopropilamidoborano-bis(r 5 -2-metil-4-bis(3,5-trifluorometil)fenilinden-1-il)circonio 1,4-difenil-1,3-butadieno, diisopropilamidoborano-bis(r 5 -3-t-butilinden-1-il)circonio 1,4-dife il-1,3-butadieno, difenilamidoborano-bis(r 5 -ciclopentadienil)circonio 1,4-difenil-1,3-butadieno, difenilamidoboranobis(r 5 -inden-1-il)circonio 1,4-difenil-1,3-butadieno, difenilamidoborano-bis(r 5 -2-metil-4-fenilinden-1-il)circonio 1,4-difenil-1,3-butadieno, difenilamidoborano-bis(r 5 -2-etil-4-fenilinden-1-il)circonio 1,4-difenil-1,3-butadieno, difenilamidoborano-bis(r 5 -2-isopropil-4-fenilinden-1-il)circonio 1,4-difenil-1,3-butadieno, d fenilamidoborano-bis(r 5 -2-metil-4-bis(3,5-trifluorometil)fenilinden-1-il)circonio 1,4-difenil-1,3-butadieno, o difenilamidoborano-bis(r 5 -3-t-butilinden-1il)circonio 1,4-difenil-1,3-butadieno.
12
Un proceso de acuerdo con la reivindicacióon 1, en el que el catalizador adicionalmente comprende un material de soporte.
13
El proceso de la reivindicacióon 1, que es una polimerizacioón en fase gaseosa continua.
14
El proceso de la reivindicacióon 13, en el que el etileno se homopolimeriza, o se copolimeriza una mezcla de olefinas C2-6.
15
El proceso de cualquiera de las reivindicaciones anteriores, en el que el polómero resultante contiene ramificaciones de cadena larga. NOTA INFORMATIVA:Conforme a la reserva del art. 167.2 del Convenio de Patentes Europeas (CPE) y a la Disposición Transitoria del RD 2424/1986, de 10 de octubre, relativo a la aplicación del Convenio de Patente Europea, las patentes europeas que designen a España y solicitadas antes del 7-10-1992, no producirán ningún efecto en España en la medida en que confieran proteccion a productos químicos y farmacéuticos como tales. Esta informacioín no prejuzga que la patente estíeonoincluída en la mencionada reserva.

Independent claims15

845 paragraphs in 25 sections, as filed

IS 2 188 235 T3

DESCRIPTION

Bridged metal complexes for gas phase polymerizations.

This invention relates to the use of certain bridging Group 4 transition metal complexes possessing a single bridging structure in a gas phase olefin polymerization catalyst. The only bridge consists of boron or aluminum atoms that are further bonded with nitrogen-containing groups. The unique bridging structures present in the complexes provide gas phase olefin polymerization catalysts with exceptionally high catalytic efficiency, and processes that provide unique properties to polymers.

In Angew. Chem. Int. Ed. Engl., 36, 21, p2338-2340 (1997) and Phosphorus, Sulfur and Silicon, 124 & 125, p561-565 (1997) described amido-substituted boron-linked ferroenophanes to form polypropylene (ferrocenes) by means of a ring-opening polymerization. In Chem. Ber., 127, p1901-1908, (1994) the synthesis and characterization of complexes of metals of Groups 1 and 2 and tin of 1,2-bis (dimethylamino) -1,2-di-9 will be described. -fluorenildiboranes. The same researchers described, in Eur. J. Inorg. Chem., P505-509 (1998), diboranes that had a similar structure to those used in the previous study. In J. Organomet. Chem., 530 p117-120 (1997) described similar bisborane ferrozenophan derivatives for further studies of molecular properties. In Organometallics, 16, p4546-4550 (1997) boron-linked metallocene ansa complexes, including dimethylslfide and phosphine adducts thereof, were described with possible utility in Ziegler-Natta type olefin polymerizations.

In the patent literature, documents EP-A-416,815 and WO 98/39369 generically describe bridging metal complexes for use as components of olefin polymerization catalysts, including complexes containing one or more boron atoms. On Bridge.

The present invention refers to the use of certain complexes of transition metals of the Bridging Group 4 as catalysts for the polymerization of olefins in a polymerization of olefins in the gas phase, where said complexes correspond to the following faormules:

Or Formula 2

Formula 1 in which:

M is titanium, zirconium, or hafnium in the +4, +3, or +2 oxidation state;

Y1 and Y2 are independently an aniic, cyclic or non-cyclic π-bonded group, NR1, PR1; NR1two or 12;

Z is boron or aluminum;

Q is a neutral, anioanic or dianioanic ligand group depending on the oxidation state of M;

j is 1, 2 or 3 depending on the oxidation state of M and the electroanic nature of Q;

T independently in each case is:

IS 2 188 235 T3

R1 is independently in each case hydrogen, a hydrocarbyl group, a tri (hydrocarbyl) silyl group, or a tri (hydrocarbyl) silylhydrocarbyl group, said R groups containing1 up to 20 atoms not counting hydrogens;

R5 is R1 oN (R1) 2; and two R groups1 together or one or more R groups1 along with R5 they can optionally be joined to form a ring structure.

It will be understood that the above metal complexes can exist as dimers and that one or more Lewis bases can optionally coordinate with the complex or dimer thereof, and that when Y1 or and2 are the neutral ligands, NR1two oPR12, the bond with M is a coordinate covalent bond rather than a covalent bond. Also, when T is R12N and Z is boron, the bond between T and Z, particularly in the compounds of formula 1, may possess double bond characteristics, that is, the resulting group is more exactly represented by the formula R12N = B. In addition, suitable catalyst compositions desirably further comprise an activating cocatalyst and a support.

The above metal complexes are produced by the reaction of a metallized derivative of a compound of one of the formulas:

VR4 /Y"*4τ_z/ T — Z T \ T-X

Formula 1A or Formula 2A where Z, T, R1 yR5 they are as defined above;

Y1 and Y2 are an anionic, cyclic or non-cyclic π-bonded group, NR1 or PR1;

Y

R4 is hydrogen or a trimethylsilyl group, with a metal salt of formula MY34, where M is a Group 4 metal, and Y3 it is a leaving group, especially halide. The reagents can be combined as neat reagents or in an inert solvent. Temperatures of -100 C to 150 C are preferred.

In a particularly preferred embodiment, the formula 1 and formula 2 complexes are prepared in high racemic purity in the +2 formal oxidation state by contacting the metallized derivatives of the formula 1A or formula 2A compounds with a precursor of the Group 4 of the formula

IS 2 188 235 T3

R6

Formula 3 where M and Y3 are as defined above,

R6, independently in each case, is hydrogen, a hydrocarbyl group, a tri (hydrocarbyl) silyl group, or a tri (hydrocarbyl) silylhydrocarbyl group, said R groups containing6 up to 20 atoms not counting hydrogens; Y

LB is a Lewis base, especially an ether, amine, or phosphine of up to 20 carbons.

The complexes are desirably prepared in an inert solvent, especially an aliphatic or aromatic or ether hydrocarbon, employing temperatures of -100 ° C to 150 ° C. This technique is similar to that described in US Patent Application 265,641, filed March 10, 1999, differing in that different starting reagents are used.

The process of the present invention can be used in combination with one or more additional polymerization processes in parallel or in series, using the same or different reactors.

As the catalyst compositions possess improved catalyst efficiencies and improved thermal stability, they are particularly suited to use with higher operating temperatures and poor heat transport conditions, such as those commonly encountered under gas phase polymerization conditions.

All references to the Periodic Table of the Elements in this document will refer to the Periodic Table of the Elements, protected by copyright and published by CRC Press, Inc., 1997. In addition, any reference to a Group or Groups is will refer to the Groups or Groups reflected in this Periodic Table of the Elements using the IUPAC system to number the groups. By the term "π-bonded", as used herein, it is meant that the binding occurs through an interaction involving delocalized electrons. Finally, by the expression, "leaving group" is meant a ligand that is easily displaced by another ligand under conditions of ligand exchange.

The present Group 4 transition metal complexes contain a unique bridging group: (TZ) or (TZ) 2, which imparts improved catalytic properties when used in combination with one or more activating cocatalysts or activating techniques in the presence of monomers polymerizable by addition. While not wishing to be limited by any theory, it is believed that the improvement in catalytic properties for such complexes may be due to the electron donation or electron extraction properties of the Y residues.1 hey2.

Preferred Group 4 transition metal complexes are those that correspond to formula 1 or 2 and are represented in phaormules 4, 5, 6, 7, 8 and 9:

IS 2 188 235 T3

Rtwo is hydrogen, or a hydrocarbyl, halohydrocarbyl, dihydrocarbylaminohydrocarbyl, tri (hydrocarbylsilyl) hydrocarbyl group, Si (R3) 3, N (R3) 2, or OR3 up to 20 carbon or silicon atoms, and optionally two R groups can be joined together2 adjacent thereby forming a fused ring structure, especially an indenyl ligand or a substituted indenyl ligand; YR3 is independently hydrogen, a hydrocarbyl group, a trihydrocarbylsilyl group or a trihydrocarbylsilylhydrocarbyl group, said R having3 up to 20 atoms not counting hydrogens.

When M is in the oxidation state +4, j = 2 and Q independently in each case is halide, hydride, hydrocarbyl, silylhydrocarbyl, hydrocarbyl oxide, dihydrocarbylamide, said Q having up to 20 aotomes without counting hydrogens. Alternatively, two Q groups can be joined together to form an alkanediyl group or a conjugated C4-40 diene ligand that coordinates with M in a metallocyclopentene form.

When M is in the oxidation state +3, j = 1 and Q is 1) a monovalent anioonic stabilizing ligand selected from the group consisting of alkyl, cycloalkyl, aryl, silyl, amido, phosphido, alkoxy, aryloxy, sulfido and mixtures thereof, and which was additionally substituted with an amine, phosphine, ether or thioether containing a substituent capable of forming a coordinated covalent bond or a chelating bond with M, said ligand having up to 50 aotomes without counting the hydrogens; or 2) a C3-10 hydrocarbyl group comprising an ethylogenic unsaturation capable of forming an η bond3 with M.

When M is in the +2 oxidation state, j = 1 and Q is a neutral conjugated diene, optionally substituted with one or more tri (hydrocarbyl) silyl or tri (hydrocarbylsilyl) hydrocarbyl groups, said Q having up to 40 carbon atoms and forming a π complex with M.

In formulas 4a-9a presented below, where the definitions of M, Z, R1, R2 yR3 are as defined above, specific examples of the above metal complexes are shown in which M is in the +4 oxidation state:

IS 2 188 235 T3

where Q, independently in each case is a halide, hydrocarbyl, hydrocarbyloxy or dihydrocarbylamide group of up to 10 atoms not counting hydrogens, or two Q groups together form a diene ligand C4-20 coordinated with M in a form of metallocyclopentene. Most preferably Q, independently in each case, is a chloride or a C1-6 hydrocarbyl group, or two Q groups together form a 2-methyl-1,3-butadienyl or 2,3-dimethyl-1,3-group. butadienyl.

In formulas 4b-9b presented below, where the definitions of M, Z, R1, R2 yR3 are as defined above, specific examples of the above metal complexes are shown in which M is in the +3 oxidation state:

IS 2 188 235 T3

where Q, in each case is a monovalent anionic stabilizing ligand selected from the group consisting of alkyl, cycloalkyl, aryl and silyl groups, which are additionally substituted with one or more amine, phosphine or ether substituents capable of forming a coordinated covalent bond or a chelating bond with M, said Q having up to 30 atoms other than hydrogen; or Q is a C3-10 hydrocarbyl group comprising an ethylenic unsaturation capable of forming an η bond3 with M. More preferred examples of said Q ligands are 2-N, N-dimethylaminobenzyl, allyl and 1-methyl-allyl.

In the formulas 4c-9c presented below, where the definitions of M, Z, R1, R2 yR3 are as defined above, specific examples of the above metal complexes in which M is in the +2 oxidation state are shown:

ES 2 188 235 T3 where Q, in each case is a neutral conjugated diene, optionally substituted with one or more tri (hydrocarbyl) silyl or tri (hydrocarbyl) silylhydrocarbyl groups, said Q having up to 30 atoms without counting the hydrogens and forming a complex π with M. The most preferred Q groups are 1,4-diphenyl-1,3-butadiene,

1,3-pentadiene, 3-methyl-1,3-pentadiene, 2,4-hexadiene, 1-phenyl-1,3-pentadiene, 1,4-dibenzyl-1,3-butadiene,

1,4-ditolyl-1,3-butadiene, 1,4-bis (trimethylsilyl) -1,3-butadiene and 1,4-dinaphthyl-1,3-butadiene.

Preferably, in the above formulas, R1 independently in each case it is C1-4 alkyl or phenyl, more preferably methyl or isopropyl, even more preferably methyl, both Y1 as Y2 are inden-1-yl, 2-alkyl-4-arylinden-1-yl, or 3-alkylinden-1-yl, or Y1 is cyclopentadienyl or cyclopentadienyl substituted with alkyl and Y2 is fluorenyl; Z is boron and Q is halide, alkyl, N, N-dialkylamido or 1,4-diphenyl-1,3-butadiene (said alkyl or aryl groups having up to 10 carbons). Even more preferably, in formulas 4a-c and 8a-c, M is zirconium or hafnium and R1 it is methyl or isopropyl, even more preferably methyl.

During the synthesis of these complexes, the use of methyl groups R1 provides high, often quantitative, yields of the rac isoomer.

In the formulas 5a-c, 6a-c, 8a-c and 9a-c, M is even more preferably titanium, Z is boron and R1 it is C 1-4 alkyl or phenyl, further preferably methyl or isopropyl.

The most preferred metal complexes are those of formulas 4a-c and 8a-c, where both Y1 as Y2 are inden-1-yl, 2-methyl-4-phenylinden-1-yl, 3-isopropylinden-1-yl, or 3-t-butylinden-1-yl groups, especially compositions comprising more than 90 percent of the isomer rac.

Specific, but not limiting metal complexes are included in the invention and described in the previous formulas:

dimethylamidoborane-bis-Ti dichloride5-cyclopentadienyl zirconium;

dimethylamidoborane-bis-r |5-cyclopentadieiiyl zirconium dimethyl;

dimethylamidoborane-bis-Tf-cyclopentadienyl zirconium bis-dimethylamide;

dimethylamidoborane-bis-r |5-cyclopentadienyl zirconium 2-methyl-1,3-butadiene;

dimethylamidoborane-bis-r |5-cyclopentadienyl zirconium 2,3-dimethyl-1,3-butadiene; dimethylamidoborane-bis-Tf-cyclopentadienyl zirconium 2-N, N-dimethylaminobenzyl; dimethylamidoborane-bis-r |5-cyclopentadienyl zirconium allyl;

dimethylamidoborane-bis-r |5-cyclopentadjenyl zirconium Ti4-l, 4-diphenyl-1,3-butadiene; dimethylamidoborane-bis-Ti5-cyclopentadienyl zirconium r |4-2,4-hexadiene; dimethylamidoborane-bis-Ti5-cyclopentadienyl zirconium i]4-l, 4-dinaphthyl-l, 3-butadiene; dimethylamidoborane-bis-r |5-cyclopentadienyl zirconium T |4-l-phenyl-1,3-pentadiene; dimethylamidoborane-bis-T |5-cyclopentadienyl zirconium T}5-l, 3-pentadiene; dimethylamidoborane-bis-Tf-n-butylcyclopentadienyl zirconium dichloride; dimethylamidoborane-bis-T ^ -n-butylcyclopentadienyl zirconium dimethyl; bis-dimethylamidoborane-bis-r bis-dimethylamide |5-n-butylcyclopentadieml zirconium; dimethylamidoborane-bis-T]5-n-butylcyclopentadienyl zirconium 2-methyl-1,3-butadiene; dimethylamidoborane-bis-r |5-n-butylcyclopentadienyl zirconium 2,3-dimethyl-1,3-butadiene; dimethylamidoborane-bis-r |s-n-butylcyclopentadienyl zirconium 2-N, N-dimethylaminobenzyl; dimethylamidoborane-bis-r |5-n-butylcyclopentadienyl zirconium allyl; dimethylamidoborane-bis-T)5-n-butylcyclopentadienyl zirconium r |4-l, 4-diphenyl-1,3-butadiene; dimethylamidoborane-bis-rf-n-butylcyclopentadieiiyl zirconium r |4-2,4-hexadiene; dimethylamidoborane-bis-Tf-n-butylcyclopentadienyl zirconium η4-1,4-dinaphthyl-1,3-butadiene;

ES 2 188 235 T3 dimethylamidoborane-bis-h5-n-butylcyclopentadienyl zirconium η4 -1-phenyl-1,3-pentadiene; dimethylamidoborane-bis-r |5-n-butylcyclopentadieml zirconium η5-1,3-pentadiene; dimethylamidoborane-bis-T ^ -inden-l-ylzirconium dichloride;

dimethylamidoborane-bis-ri5-inden-1 -ylzirconium dimethyl;

bis-dimethylamidoborane-bis-r bis-dimethylamide |5-¡Nden-l-ilzirconium;

dimethylamidoborane-bis-T |5-inden-l-ylzirconium 2-methyl-1,3-butadiene;

dimethylamidoborane-bis-T |5-inden-l-ylzirconium 2,3-dimethyl-1,3-butadiene;

dimethylamidoborane-bis-Ti'-inden-1 -ylzirconium 2-N, N-dimethylaminobenzyl;

dimethylamidoborane-bis-T]5-inden-l -ylzirconium allyl;

dimethylamidoborane-bis-r |5-inden-1 -ylzirconium η4-1,4-diphenyl-1,3-butadiene;

dimctylamidoborane-bis-T |5-inden-l-ilzirconium T |4-2,4-hexadiene;

dimethylamidoborane-bis-T |5-indeii-1 -ilzirconium η4-1,4-dinafyl-1,3-butadiene;

dimethylamidoborane-bis-T |5-inden-l-ilcircomo Ti4-l-phenyl-l, 3-pcntadiene;

dimethylamidoborane-bis-T |5-inden-l-ilzirconium n4-l, 3-pentadiene;

dimethylamidoborane-bis-r dichloride |5- (2-methylinden-l-yl) zirconium;

dimctylamidoborane-bis-Ti5- (2-methylinden-l-yl) zirconium dimethyl;

Dimethylamidoborane-bis-T bis-dimethylamide)5- (2-methylinden-l-yl) zirconium;

dimethylaniidoborane-bis-T |5- (2-methylinden-l-yl) zirconium 2-methyl-l, 3-butadiene;

dimethylamidoborane-bis-Ti5- (2-Inethylinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene; dimethylamidoborane-bis-T |5- (2-Methylinden-l-yl) zirconium 2-N, N-dimethylaminobenzyl; dimethylamidoborane-bis-r |5- (2-methylinden-1 -yl) allyl zirconium;

dimethylamidoborane-bis ^5- (2-methylinden-l-yl) zirconium r |4-l, 4-diphenyl-1,3-butadiene; dimethylamidoborane-bis-r |5- (2-methylinden-l -yl) zirconium r |4-2,4-hexadiene; dimethylamidoborane-bis-r |5- (2-methylinden-l -yl) zirconium η4-1,4-dinaphthyl-1,3-butadiene; dimethyl ainidoborane-bis-T |5- (2-methylinden-l -yl) zirconium η4-1-phenyl-1,3-pentadiene; dimethylamidoborane-bis-T |5- (2-methylinden-l-yl) zirconium |4-l, 3-pentadiene; dimethylamidoborane-bis-r dichloride |5- (2-Inethyl-4-femlinden-l-yl) zirconium; dimethylamidoborane-bis-Ti5- (2-methyl-4-phenylinden-l-yl) zirconium dimethyl; Dimethylamidoborane-bis-T bis-dimethylamide |5- (2-methyl-4-phenylinden-l-yl) zirconium; dimethylamidoborane-bis-Ti5- (2-methyl-4-phenylinden-l-yl) zirconium 2-methyl-l, 3-butadiene; dimethylamidoborane-bis-Ti5- (2-methyl-4-phenylinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene; dimethylamidoborane-bis-Ti5- (2-mctyl-4-phenylinden-1-yl) zirconium 2-N, N-dimethylaminobenzyl; dimethylamidoborane-bis-Ti5- (2-methyl-4-phenylinden-l-yl) allyl zirconium; dimethylamidoborane-bis-T |5- (2-methyl-4-phenylinden-l-yl) zirconium |4-l, 4-diphenyl-1,3-butadiene; dimethylamidoborane-bis-'q5- (2-methyl-4-phenylinden-l-yl) zirconium T |4-2,4-hexadiene; dnnethylamidoborane-bis-T |5- (2-methyl-4-phenylinden-l-yl) zirconium T |4-l, 4-dinafil-l, 3-butadiene; dimethylamidoborane-bis-r |5- (2-methyl-4-phenylinden-l-yl) zirconium r |4-l-phenyl-l, 3-pcntadiene; dimethylamidoborane-bis-T |5- (2-methyl-4-phenylinden-l-yl) zirconium η4-1,3-pentadiene; diinethylamidoborane-bis dichloride ^5- (2-ethyl-4-phenylinden-l-yl) zirconium; dimethylamidoborane-bis-Tis- (2-ethyl-4-phenylinden-1 -yl) zirconium dimethyl; Dimethylamidoborane-bis bis-dimethylamide ^5- (2-ethyl-4-phenylinden-l-yl) zirconium; dimethylamidoborane-bis-r |5- (2-ethyl-4-phenylinden-1-yl) zirconium 2-methyl-1,3-butadiene;

ES 2 188 235 T3 cyl;

diene;

dimethylamidoborane-bis-q5- (2-ethyl-4-phenylinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene; dimethylamidoborane-bis-T,5- (2-ethyl-4-phenylinden-l-yl) zirconium 2-N, N-dimethylaminobenzyl; dimethylamidoborane-bis-r |5- (2-ethyl-4-phenylinden-l-yl) allyl zirconium;

dimethylamidoborane-bis-Ti5- (2-ethyl-4-phenylinden-l-yl) zirconium r |4-l, 4-diphenyl-1,3-butadiene; dimethylamidoborane-bis-r |5- (2-ethyl-4-phenylinden-l-yl) zirconium r / -2,4-hexadiene; dimethylamidoborane-bis-p5- (2-ethyl-4-phenylinden-l-yl) zirconium T |4-l, 4-dinaphthyl-l, 3-butadiene; dimethylamidoborane-bis-T |5- (2-ethyl-4-phenylinden-1-yl) zirconium η4-1-phenyl-1,3-pentadiene; dimethylamidoborane-bis-T |5- (2-ethyl-4-phenylinden-I-¡l) zirconium q4-l, 3-pentadiene; dimethylamidoborane-bis-r dichloride |5- (2-isopropyl-4-phenylinden-l-yl) zirconium; dimethylamidoborane-bis-q5- (2-isopropyl] -4-phenylinden-l-yl) zirconium dimethyl; bis-dimethylamidoborane-bis-p bis-dimethylamide5- (2-isopropyl-4-phenylinden-l-yl) zirconium; dimethylamidoborane-bis-q5- (2-isopropyl-4-phenylinden-1-yl) zirconium 2-methyl-1,3-butadiene; dimethylamidoborane-bis-n5- (2-isopropyl-4-phenylinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene; dimethylainidoborane-bis-Ti5- (2-isopropyl] -4-phenylinden-l-yl) zirconium 2-N, N-dimethylaminobenedimethylamidoborane-bis-r |5- (2-isopropyl-4-phenylinden-l-yl) allyl zirconium; dimctylamidoborane-bis-r |5- (2-isopropyl-4-phenylinden-1-yl) zirconium η4-1,4-diphenyl-1,3-butadimethylamidoborane-bis-T / - (2-isopropyl-4 ~ phenylinden-1-yl) zirconium T |4-2,4-hexadiene; dimethylamidoborane-bis-T |5- (2-isopropyl-4 "phenylinden-1-yl) zirconium η4-1,4-dinaphthyl-1,3-butadimethylamidoborane-bis-q5- (2-isopropyl-4-phenylinden-1-yl) zirconium η4-1-phenyl-1,3-pentadimethylamidoborane-bis-q5- (2-isopropyl-4-phenylinden-l-yl) zirconium T |4-l, 3-pentadiene; dimethylamidoborane-bis-p dichlorides- (2-methyl-4-naphthylinden-l-yl) zirconium; dimethylamidoborane-bis-T |5- (2-methyl-4-naphthylinden-1-yl) zirconium dimethyl; bis-dimethylamidoborane-bis-r bis-dimethylamide |5- (2-methyl-4-naphthylinden-l-yl) zirconium; dimethylamidoborane-bis-Tis- (2-methy] -4-naphthylinden-l-yl) zirconium 2-methyl-l, 3-butadiene; dimethylamidoborane-bis-r |5- (2-methyl-4-naphthylinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene; dimethylamidoborane-bis-p5- (2-methyl-4-naphthylinden-l-yl) zirconium 2-N, N-dimethylaminobenzyl; dimethylamidoborane-bis-q5- (2-methyl-4-naphthylinden-l-yl) allyl zirconium; dimethylamidoborane-bis-T |5- (2-methyl-naphthylinden-l-Il) zirconium q4-l, 4-diphenyl-1,3-butadiene; dimethylamidoborane-bis-p5- (2-methyl-naphthylinden-l-yl) zirconium p4-2,4-hexadiene; dimethylamidoborane-bis-p5- (2-methyl-naphthylinden-l-yl) zirconiumq4-l, 4-dinnyl-l, 3-butadiene; dimethylamidoborane-bis-Ti5- (2-methyl-naphthylinden-l-yl) zirconium q4-l-fcnyl-l, 3-pentadiene; dimethylamidoborane-bis-q5- (2-methyl-naphthylinden-l-yl) zirconium q4-l, 3-pentadiene; dimethylamidoborane-bis-p dichloride5- (2-methyl-4-bis (3,5-trifluoromethyl) phenylinden-lyl) zirconium;

dimethylamidoborane-bis-r |5- (2-methyl-4-bis (3,5-trifluoromethyl) phenylinden-1-yl) zirconium dimethyl;

Dimethylamidoborane-bis-p bis-dimethylamide5- (2-methyl-4-bis (3,5-trifluoromethyl) phenylindenl-yl) zirconium;

ES 2 188 235 T3 dimethylamidoborane-bis-T |S- (2-methyl-4-b¡s (3,5-trifluoromethyl) phenylinden-l-yl) zirconium-2-methyl-1,3-butadiene;

dimethylamidoborane-bis-n5- (2-methyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene;

dimethylamidoborane-bis-r |5- (2-methyl-4-bis (3,5-trifluoro-methyl) phenylinden-l-yl) zirconium 2-N, N-dimethylaminobenzyl;

dimethylamidoborane-bis ^5- (2-methyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium allyl; dimethylamidoboraiio-bis-n5- (2-methyl-4-bis (3,5-trifluoromethyl) fcnilinden-l-yl) zirconium η4-1,4-diphenyl-1,3-butadiene;

dimethylamidoborane-bis-n5- (2-methyl-4-bis (2-inethyl-4-bis (3,5-trifluoromellyl) phenylinden-lyl) zirconium r |4-2,4-hexadiene;

dimethylamidoborane-bis-Ti5- (2-Inethyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zircomo η4-1,4-dinaphthyl-1,3-butadiene;

dimethylamidoborane-bis-Ti5- (2-methyl-4-bis (3,5-trifluoromethyl) phenylindcn-1-yl) zirconium η4-1-phenyl-1,3-pentadiene;

dimethylamidoborane-bis-r |5- (2-methyl-4-bis (3,5-trifluoromethyl) phenylinden-1-yl) zirconium η4-1,3pentadiene;

dimethylamidoborane-bis-r dichloride |5- (2-ethyl-4-bis (3,5-trifluoromethyl) pheiiilinden-lyl) zirconium;

dimethylamidoborane-bis-T |5- (2-ethyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zircomo dimethyl; bis-dimethylamidoborane-bis-r bis-dimethylamide |5- (2-ethyl-4-bis (3,5-trifluoromethyl) phenylinden-lyl) zirconium;

dimethylainidoborane-bis ^5- (2-ethyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium 2-methyl1.3-butadiene;

dimethylamidoborane-bis-r |5- (2-ethyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene;

dimethylamidoborane-bis-n5- (2-ethyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium 2-N, N-dimethylaminobenzyl;

dimethylamidoborane-bis-r |5- (2-ethyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium allyl; dimethylamidoborane-bis-T |5- (2-ethyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium η4-1.4 · 4ϊphenyl-1,3-butadiene;

dimethylamidoborane-bis-T |5- (2-ethyl-4-bis (2-methyl-4-bis (3,5-trifluoromethyl) phenylinden-lyl) zirconium r |4-2,4-hexadiene;

dimethylamidoborane-bis-T |5- (2-ethyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium η4-1,4-άίnaphthyl-1,3-butadiene;

dimethylamidoborane-bis ^5- (2-ethyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium η4-1-phenyl1.3-pentadiene;

dimethylamidoborane-bis-r |5- (2-ethyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium η4-1,3pentadiene;

dimethylamidoborane-bis-r dichloride |5- (2-isopropyl-4-bis (3,5-trifluoromethyl) femlinden-l yl) zirconium;

dimethylamidoborane-bis-T |5- (2-isopropyl-4-bis (3,5-trifluoromethyl) phenylinden-II]) zircomo dimethyl;

ES 2 188 235 T3 dimethylainidoborane-bis-n bis-dimethylamide5- (2-isopropyl-4-bis (3,5-trifluoromethyl) phenylinden-1-yl) zirconium;

dimethylamidoborane-bis-q5- (2-isopropyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) circoiiio 2-methyl-1,3-butadiene;

diinethylainidoborane-bis-q5- (2-isopropyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene;

diinethylainidoborane-bis-q5- (2-isopropyl-4-bis (3,5-trifluoromethyl) phenylinden-1-yl) zirconium 2N, N-dimethylaminobenzyl;

dimethylamidoborane-bis-q5- (2-isopropyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium aillo;

dimethylamidoborane-bis-T |5- (2-isopropyl-4-bis (3,5-trifluoromethyl) phenylinden-li]) zirconium η41,4-diphenyl-1,3-butadiene;

dimethylamidoborane-bis-p5- (2-isopropyl-4-bis (2-methyl-4-bis (3,5-trifluoromethyl) phenylinden-lyl) zirconium q4-2,4-hexadiene;

dimethylamidoborane-bis-q5- (2-isopropyl-4-bis (3,5-trifluoromethyl) phenylinden-1-yl) zirconium η41,4-dinaphthyl-1,3-butadiene;

dimethylamidoborane-bis-n5- (2-isopropyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium η41 -phenyl-1,3-pentadiene;

dimethylamidoborane-bis-r |5- (2-isopropyl-4-bis (3,5-trifluoroiOmethyl) phenylinden-l-yl) zircomo η41,3-pentadiene;

dimethylamidoborane-bis-q dichloride5- (3-isopropylinden-l-yl) zirconium; dimethylamidoborane-bis-T |5- (3-Isopropylinden-1-yljzirconium dimethyl; bis-dimethylamidoborane-bis-q5- (3-isopropylinden-l-yl) zirconium; dimethylamidoborane-bis-T |5- (3-isopropylinden-1-yl) zirconium 2-methyl-1,3-butadiene; dimethyl amidoborane-bis-r |5- (3-Isopropylinden-1-yljzirconium 2,3-dimethyl-1,3-butadiene; dimethylamidoborane-bis-q5- (3-isopropylinden-l-yl) zirconium 2-N, N-dimethylaminobenzyl; dimethylamidoborane-bis-q5- (3-isopropylinden-l-yl) allyl zirconium; dimethylamidoborane-bis-q5- (3-isopropylinden-1-yl) zirconium η4-1,4-diphenyl-1,3-butadiene; dimethylamidoborane-bis-Ti5- (3-isopropylinden-l-yl) zirconiumT |4-2,4-hexadiene; dimethylamidoborane-bis-q5- (3-isopropylinden-1-yl) zirconium η4-1,4-dinaphthyl-1,3-butadiene; dimethylamidoborane-bis-T |5- (3-isopropylinden-1-yl) zirconium η4-1-phenyl-1,3-pentadiene; dimethylamidoborane-bis-r |5- (3-isopropylinden-1-yl) zirconium η4-1,3-pentadiene; dimethylamidoborane-bis-q dichloride5- (3-t-butylinden-l-yl) zirconium; dimethylamidoborane-bis-r |5- (3-t-butylinden-l-yl) zirconium dimethyl; Dimethylamidoborane-bis-q bis-dimethylamide5- (3-t-butylinden-l-yl) zirconium; dimethylamidoborane-bis-T |5- (3-t-Butylinden-1-yl) zirconium 2-methyl-1,3-butadiene; di methylamidoborane-bis-η5- (3-t-Butylinden-1-yl) zircomo 2,3-dimethyl -1,3-butadiene; dimethylamidoborane-bis-T |5- (3-t-butylinden-l-yl) zirconium 2-N, N-dimethylaminobenzyl; dimethylamidoborane-bis-r |5- (3-t-butylinden-l-yl) allyl zirconium; dimethylamidoborane-bis-η5- (3-t-butylinden-1 -yl) zirconium η4-1,4-diphenyl-1,3-butadiene; dimethylamidoborane-bis-q5- (3-t-butylinden-l-yl) zirconium q4-2,4-hexadiene; dimethylamidoborane-bis-r |5- (3-t-butylinden-l-yl) zirconium |4-l, 4-dinaphthyl-l, 3-butadiene;

ES 2 188 235 T3 diinethylamidoborane-b¡sq5- (3-t-butylinden-l-yl) zirconium -rl-l-phenyl-lT-pentadiene, dimethylamidoborane-bis-ri5- (3-t-butylinden-l-yl) zirconiumT | 'l-l, 3-pentadiene; diisopropylamidoborane-bis © -cyclopentadienylzirconium dichloride; diisopropylamidoborane-bis-p5-cyclopentadienylzirconium dimethyl; Diisopropylamidoborane-bis-p bis-dimethylamide5-cyclopentadienylzirconium; diisopropylamidoborane-bis-iy-cyclopentadienylzirconium 2-methyl-1,3-butadiene; diisopropylamidoborane-bis-p5-cyclopentadienylzirconium 2,3-dimethyl-1,3-butadiene; diisopropylamidoborane-bis-u5-cyclopentadienylzirconium 2-N, N-dimethylaminobenzyl; diisopropylamidoborane-bis-η5-cyclopentadienylzirconium allyl; diisopropylamidoborane-bis-q5-cyclopentadienylzirconium η4-1,4-diphenyl-1,3-butadiene; diisopropylamidoborane-bis © -cyclopentadienylzirconium q4-2,4-hexadiene; diisopropylainidoboraiio-bis-T |5-cyclopentadienylzirconium η4-1,4-dinaphthyl-1,3-butadiene; diisopropylamidoborane-bis-q5-cyclopentadienylzirconium q4-l-feml-l, 3-pentadiene; diisopropylamidoborane-bis © -cyclopentadienylzirconium Tf-1, 3-pentadiene; diisopropylamidoborane-bis-q dichloride5-inden-l-ilzirconium; diisopropylamidoborane-bis-r,s-inden-l -ylzirconium dimethyl;

diisopropylamidoborane-bis © -inden-l-ylzirconium bis-dimethylamide;

diisopropylamidoborane-bis-q5-inden-1 -ylzirconium 2-methyl-1,3-butadiene;

diisopropylamidoborane-bis-r |5-inden-l-ylzirconium 2,3-dimethyl-1,3-butadiene; diisopropylamidoborane-b¡sT |5-inden-l-ylzirconium 2-N, N-dimethylaminobenzyl; diisopropylamidoborane-bis-n'-inden-1-ylzirconium allyl;

diisopropylamidoborane-bis-T |5-inden-l-ilzirconium r |4-l, 4-difeml-l, 3-butadiene; diisopropylamidoborane-bis-T |5-inden-l -ilzirconium n4-2,4-hexadiene; diisopropylamidoborane-bis © -inden-l-ylzirconium T |4-l, 4-dinaphthyl-l, 3-butadiene; diisopropylamidoborane-bis-q5-inden-l-ilzirconium Ti4-l-phenyl-1,3-pentadiene; diisopropylamidoborane-bis-Ti5-inden-l-ilzirconiumT |4-l, 3-pentadiene; diisopropylamidoborane-bis-r dichloride |5- (2-methylinden-l-yl) zirconium; diisopropylamidoborane-bis-T |5- (2-methylinden-l-yl) zirconium dimethyl; bis-diisopropylamidoborane-bis-r bis-dimethylamide |5- (2-methylinden-l-yl) zirconium; diisopropylamidoborane-bis-q5- (2-methylinden-l-yl) zirconium 2-methyl-l, 3-butadiene; diisopropylamidoborane-bis-r |5- (2-methylinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene; diisopropylamidoborane-bis-n5- (2-methylinden-l-yl) zirconium 2-N, N-dimethylaminobenzyl; dnsopropylamidoborane-bis-r |5- (2-methylinden-1 -yl) allyl zirconium; diisopropylamidoborane-bis-r |5- (2-methylinden-l -yl) zirconium η4-1,4-diphenyl-1,3-butadiene; diisopropylamidoborane-bis-p5- (2-methylinden-l-yl) zircomo r |4-2,4-hexadiene; diisopropylamidoborane-bis © - (2-methylinden-l-yl) zirconium η4-1,4-dinaphthyl-1,3-butadiene; diisopropylamidoborane-bis-r |5- (2-methylinden-l-yl) zircomo η4-1-phenyl-1,3-pentadiene; diisopropylamidoborane-bis ^5- (2-methylinden-l-yl) zirconium T |4-l, 3-pentadiene; diisopropylamidoborane-bis dichloride ^5- (2-methyl-4-phenylinden-1-yl) zirconium; diisopropylamidoborane-bis © - (2-methyl-4-phenylinden-1-yl) zirconium dimethyl; Diisopropylamidoborane-bis-q bis-dimethylamide5- (2-methyl-4-femlinden-l -yl) zirconium; diisopropylamidoborane-bis-η5- (2-methyl-4-phenylinden-l-yl) zirconium 2-methyl-l, 3-butadiene;

ES 2 188 235 T3 diisopropylamidoborane-bis-Tf- (2-mctyl-4-phenylinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene; diisopropylamidoborane-bis-T |5- (2-Niethyl-4-phenylinden-l-yl) zirconium 2-N, N-dimethylaminobenzyl;

diisopropylamidoborane-bis © - (2-methyl-4-phenylinden-1-yl) zirconium aillo; diisopropylamidoborane-bis-r |5- (2-methyl-4-phenylinden-l-yl) zirconium ^ -l, 4-difeml-l, 3-butadiene;

diisopropdamidoborane-bis-T |5- (2-Inethyl-4-phenylinden-l-yl) c¡rcomoT |4-2,4-hexadiene; diisopropylamidoborane-bis-η5- (2-methyl-4-phenylinden-1-yl) zirconium η4-1,4-dinaphthyl-1,3-butadiene;

diisopropylamidoborane-bis-η 5- (2-methyl-4-phenylinden-l -yl) zirconium η4-1-phenyl-1,3-pentadiene; diisopropylamidoborane-bis-g5- (2-methyl-4-phenylinden-l-yl) zirconium q4-l, 3-pentadiene; diisopropylamidoborane-bis-q dichloride5- (2-methyl-4-naphthylinden-l-yl) zirconium; diisopropylamidoborane-bis-Ti5- (2-methyl-4-naphthylinden-l-yl) zirconium dimethyl; bis-diisopropylamidoborane-bis ^ dimethylamide5- (2-methyl-4-naphthylinden-l-yl) zirconium; diisopropylamidoborane-bis-n5- (2-methyl-4-nanylinden-l-yl) zirconium 2-methyl-l, 3-butadiene; diisopropylamidoborane-bis-H5- (2-methyl-4-naitilinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene; diisopropylamidoborane-bis-Ti5- (2-methyl-4-naphthylinden-l-yl) zirconium 2-N, N-dimethylaminobenzyl;

diisopropylamidoborane-bis-n5- (2-methyl-4-nanylinden-l-yl) allyl zirconium; diisopropylamidoborane-bis-g5- (2-methyl-4-naphthylinden-l-yl) zirconium T |4-l, 4-diphenyl-1,3-butadiene;

diisopropylamidoborane-bis-Ti5- (2-methyl-4-naphthylinden-l-yl) zirconium r |4-2,4-hexadiene; diisopropylamidoborane-bis-p5- (2-methyl-4-naphthylinden-l-yl) zirconium ri4-l, 4-dinaphthyl-l, 3-butadiene;

diisopropylamidoborane-bis-η 5- (2-methyl-4-naphthylinden-l-yl) zirconium η4-1-Γβηί1-1,3-ρβη (3 £ ΐϊεηο; diisopropylamidoborane-bis ^5- (2-methyl-4-naphthylinden-l-yl) zirconium η4-1,3-ρβηΐ3 <ΰεηο; diisopropylamidoborane-bis dichloride ^5- (2-methyl-4- (3,5-dimethylphenyl) inden-1-yl) zirconium; diisopropylamidoborane-bis ^5- (2-methyl-4- (3,5-dimethylphenyl) inden-l-yl) zirconium dimethyl; bis-diisopropylamidoborane-bis ^ dimethylamide5- (2-methyl-4- (3,5-dimethylphenyl) inden-lyl) zirconium;

diisopropylamidoborane-bis ^5- (2-methyl-4- (3,5-dimethylpheml) inden-1-yl) zirconium 2-methyl-1,3butadiene;

dnsopropylamidoborane-bis-n5- (2-methyl-4- (3,5-dimethylphenyl) linden-l-l) zirconium 2,3-dimethyl-1,3-butadiene;

diisopropylamidoborane-bis ^5- (2-methyl-4- (3,5-dimethylphenyl) linden-1-yl) zirconium 2-N, N-dimethylaminobenzyl;

diisopropylamidoborane-bis-n5- (2-methyl-4- (3,5-dimethylphenyl) inden-l-yl) allyl zirconium; diisopropylamidoborane-bis ^5- (2-methyl-4- (3,5-dimethylphenyl) inden-l-yl) zircomo η4-1.4- <1ίίεnyl -1.3 -butadiene;

diisopropylamidoborane-b¡sqs- (2-methyl-4- (3,5-dimethylphenyl) inden-l-¡l) zircomo η4-2.4-1ιεχ3diene;

diisopropylamidoborane-bis © - (2-methyl-4- (3,5-dimethylphenyl) inden-l-yl) zirconium η4-1.4 ^ ίη3ίthyl-l, 3-butadiene;

ES 2 188 235 T3 diisopropylamidoborane-bis-r |5- (2-methyl-4- (3,5-dimethylphenyl) mden-l-yl) zirconium r |4-l-phenyl1.3-pentadiene;

diisopropylamidoborane-bis-n5- (2-methyl-4- (3,5-dimethylphenyl) indcn-l-yl) zirconium r |4-l, 3-pcntadiene;

diisopropylamidoborane-bis-n dichloride5- (2-methyl-4- (3,5-dilfuoromethylphenyl) inden-1 yl) zirconium;

diisopropylainidoborane-bis-T |5- (2-methyl-4- (3,5-difluoroTnethylphenyl) inden-l-yl) zirconium dimethyl;

diisopropylamidoborane-bis ^ bis-dimethylamide5- (2-methyl-4- (3,5-difluoromethylphenyl) indenl-yl) zirconium;

diisopropylamidoborane-b¡sr |5- (2-methyl-4- (3,5-diyluoromethylphenyl) inden-1-yl) zirconium 2-methyl1.3-butadiene;

diisopropylamidoborane-bis-Ti5- (2-methyl-4- (3,5-diluoromethylphenyl) inden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene;

diisopropylamidoborane-bis-T |5- (2-methyl-4- (3)5-difluoromethylphenyl) inden-l-yl) zircomo 2-N, N-dimethylaminobenzyl;

diisopropylamidoborane-bis-r |S- (2-methyl-4- (3,5-difluoromethylpheml) inden-l-yl) zirconioalyl; diisopropylamidoborane-bis-T |5- (2-methyl-4- (3,5-difluoromethylphenyl) inden-1 -yl) zirconium η4-1,4-diphenyl-1,3-butadiene;

diisopropylamidoborane-bis-TY5- (2-methyl-4- (3,5-difluoromethylphenyl) inden-l-yl) zirconium η4-2.4hexadiene;

dnsopropylamidoborane-bis-T |5- (2-methyl-4- (3,5-difluoroinethylpheiiil) inden-l-yl) zirconium η4-1,4dinaphthyl-1,3-butadiene;

diisopropylamidoborane-bis-r |5- (2-Inethyl-4- (3,5-difluoromethylphenyl) inden-l-yl) zirconium η4-1phenyl-1,3-pentadiene;

diisopropylamidoborane-bis-T |5- (2-methyl-4- (3,5-difluoromethylphenyl) inden-l-yl) zirconium η4-1,3pentadiene;

diisopropyl dichloride] amidoborane-bis-T |5- (2-cyl-4-phenylindcn-l-yl) zirconium; di¡soprapilamidoborane-bis-Ti5- (2-ethyl-4-phenylinden-l-yl) zirconium dimethyl; bis-diisopropylamidoborane-bis-r bis-dimethylamide |5- (2-ethyl-4-phenylinden-l-yl) zirconium; diisopropylamidoborane-bis-n5- (2-ethyl-4-phenylinden-l-yl) zirconium 2-methyl-l, 3-butadiene; diisopropylamidoborane-bis-r |5- (2-ethyl-4-phenylinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene; diisopropylamidoborane-bis-r |5- (2-ethyl-4-phenylinden-l-yl) circoiiio 2-N, N-dimethylaminobenzyl; diisopropylamidoborane-bis-r |5- (2-ethyl-4-phenylinden-1-yl) allyl zirconium; diisopropylamidoborane-bis-T |5- {2-ethyl-4-phenyl] inden-1 -yl) zirconium η4-1,4-diphenyl-1,3-butadiene; diisopropylamidoborane-bis-n5- (2-ethyl-4-phenylinden-l-yl) zirconium T |4-2,4-hexadiene; diisopropylamidoborane-bis-n5- (2-ethyl-4-phenylinden-l-yl) zirconium ri4-l, 4-dinaphthyl-l, 3-butadiene;

diisopropylamidoborane-bis-r |5- (2-ethyl-4-phenylinden-l-yl) zirconium η4-1-phenyl-1,3-pentadiene; diisopropylamidoborane-bis-n5- (2-ethyl-4-phenylinden-l-yl) zirconium η4-1,3-pentadiene; diisopropylamidoborane-bis-Ti dichloride5- (2-isopropyl-4-fcnilinden-1-yl) zirconium; diisopropylamidoborane-bis-T |5- (2-isopropyl-4-phenylinden-l-l) zirconium dimethyl; diisopropylainidoborane-bis ^ bis-dimethylamide5- (2-isopropyl-4-feiulinden-l-yl) zircomo;

ES 2 188 235 T3 diisopropylanudeborane-bis-T |5- (2-isopropyl-4-phenylinden-l-yl) zirconium 2-methyl-1,3-butadiene; diisopropylamidoborane-bis ^5- (2-isopropyl-4-phenylinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene;

diisopropylamidoborane-bis-T |5- (2-isopiOpil-4-phenylinden-1-yl) zirconium 2-N, N-dimethylaminobenzyl;

diisopn> pilamidoborane-bis-T |!- (2-isopropyl-4-phenylinden-l-yl) allyl zirconium; dnsopropylamidoborane-bis-n5- (2-isopropyl-4-phenylinden-l -yl) zirconium η4-1,4-diphenyl-1,3-butadiene;

diisopropylamidoborane-bis-r |5- (2-isopropyl-4-phenylinden-l-yl) zirconior |4-2,4-hexadiene; diisopropylamidoborane-bis-r |5- (2-isopropyl-4-phenylinden-l-yl) zirconium T)4-l, 4-dinaphthyl-l, 3-butadiene;

diisopropylamidoborane-bis-r |5- (2-isopropyl-4-femlinden-l-yl) zircomo T)4-l-phenyl-1,3-pentadiene;

diisopropylamidoborane-bis-T |5- (2-isopiOpil-4-phenylinden-l-yl) zirconium r |4-l, 3-pentadiene; diisopropylamidoborane-bis-r dichloride |5- (3-isopropylinden-l-yl) zirconium; diisopropylamidoborane-bis-T |5- (3-isopropylinden-l-yl) zirconium dimethyl; bis-diisopropylamidoborane-bis ^ dimethylamide5- (3-isopropylinden-l-yl) zirconium; diisopropylamidoborane-bis-r |5- (3-isopropylinden-1-yl) zirconium 2-methyl-1,3-butadiene; diisopropylamidoborane-bis-T |5- (3-isopropylinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene; diisopropylamidoborane-bis-r |5- (3-isopropylinden-l-yl) zirconium 2-N, N-dimethylaminobenzyl; diisopropylamidoborane-bis-T |5- (3-isopropylinden-l-yl) allyl zirconium; diisopropylamidoborane-bis-r |5- (3-isopropylinden-l-yl) zirconium q4-l, 4-diphenyl-1,3-butadiene; diisopropylamidoborane-bis-r |5- (3-isopropylinden-l-yl) zircom n4-2,4-hexadiene; diisopropylamidoborane-bis-T |5- (3-isopropylinden-l-yl) zirconium q4-l, 4-dinafyl-l, 3-butadiene, dnsopropylamidoborane-bis-T |5- (3-isopropylinden-l -yl) zirconium η4- 1-phenyl-1,3-pentadiene; diisopropylamidoborane-bis-Ti5- (3-isopropyliiiden-l-yl) zirconium r |4-l, 3-pentadiene; diisopropylamidoborane-bis-T dichloride |5- (3-t-butylinden-l-yl) zirconium; diisopropylamidoborane-bis-r |5- (3-t-butylinden-l-yl) zirconium dimethyl; Diisopropylamidoborane-bis-q bis-dimethylamide5- (3-t-butylinden-l-yl) zirconium; diisopropylamidoborane-bis-q5- (3-t-butylinden-l-yl) zirconium 2-methyl-l, 3-butadiene; diisopropylamidoborane-bis-r |5- (3-t-Butylinden-1 -yljzirconium 2,3-dimethyl-1,3-butadiene; diisopropylamidoborane-bis-q5- (3-t-Butylinden-1-yl) zirconium 2-N, N-dimethylaminobenzyl; diisopropylamidoborane-bis-r |5- (3-t-Butylinden-1-yl) allyl zirconium;

diisopropylamidoborane-bis-T / - (3-t-butylinden-1 -yl) zirconium η4-1,4-diphenyl-1,3-butadiene; diisopropylamidoborane-bis-Ti5- (3-t-butylinden-1 -yl) zirconium -q4-2,4-hexadiene; diisopropylamidoborane-bis-T |5- (3-t-butylinden-1 -yl) zirconium η4-1,4-dinaphthyl-1,3-butadiene; diisopropylamidoborane-b¡sT |S- (3-t-butylinden-l-yl) zircomo η4-1-phenyl-1,3-pentadiene; diisopropylaimdoborane-bis-ηs- (3-t-butylinden-1 -yl) zirconium η4-1,3-pentadiene; diphenylamidoborane-bis-T dichloride |5-cyclopentadienyl zirconium; difchnylamidoborane-bis-r |5-cyclopentadiem] zirconium dimethyl;

diphenylamidoborane-bis-q bis-dimethylamide5-cyclopentadienyl zirconium; diphenylamidoborane-bis-q5-cyclopentadienyl zirconium 2-methyl-1,3-butadiene;

ES 2 188 235 T3 diphenylamidoborane-bis-n5-cyclopentadienyl zirconium 2,3-dimethyl-1,3-butadiene; difchnylamidoborane-bis-η5-cyclopentadienyl zirconium 2-N, N-dimethylaminobenzyl; diphenylamidoborane-bis-T |5-cyclopentadienyl zirconium allyl;

diphenylamidoborane-bis-q5-cyclopentadienyl zirconium η4-1,4-άίίεηί1-1,3-butadiene; diphenylamidoborane-bis © -cyclopentadienyl zirconium Ti4-2,4-hexadiene; diphenylamidoborane-bis-T |5-cclof> entadienyl zirconium Ti4-l, 4-dinaphthyl-l, 3-butadiene; diphenylamidoborane-bis-T |5-cyclopentadienyl zirconium T)4-l-phenyl-1,3-pentadiene; diphenylamidoborane-bis-Tf-cyclopentadienyl zirconium n4-l, 3-pentadiene; diphenylamidoborane-bis © -n-butylcyclopentadienyl zirconium dichloride; diphenylamidoborane-bis-r |5-n-butylcyclopentadienyl zirconium dimethyl; diphenylamidoborane-bis ^ bis-dimethylamides-n-butylcyclopentadienyl zirconium; diphenylamidoborane-bis-T |5-n-butylcyclopentadienyl zirconium 2-methyl-1,3-butadiene; difchnylamidoborane-bis - r,5-n-butyclopentadienyl zirconium 2,3-dimethyl-1,3-butadiene; diphenylamidoborane-bis-T |5-n-butylcyclopentadienyl zirconium 2-N, N-dimethylaminobenzyl; diphenylamidoborane-bis-r |5-n-butylcyclopentadienyl zirconium allyl; diphenylamidoborane-bis-Tf-n-butylcyclopentadienyl zirconium η4-1,4-diphenyl-1,3-butadiene; diphenylamidoborane-bis-Ti5-n-butylcyclopentadienyl zirconium T |4-2,4-hexadiene; diphenylamidoborane-bis-ri5-n-butylcyclopentadienyl zirconium η 4-l, 4-dinaphthyl-l, 3-butadiene; diphenylaniidoborane-bis-Ti5-n-but¡lcyclopentadien¡l zirconium T |4-l-phenyl-1,3-pentadiene; diphlamidoborane-bis © -n-butylcyclopentadienyl zirconium r |4-l, 3-pentadiene; diphenylamidoborane-bis © -inden-l-ylzirconium dichloride; diphenylamidoborane-bis-Ti5-inden-l-ylzirconium dimethyl;

diphenylamidoborane-bis-p bis-dimethylamide5-inden-l-ilzirconium;

diphenylamidoborane-bis-η 5-inden-1 -ylzirconium 2-methyl-1,3-butadiene;

diphenylamidoborane-bis-r |5-inden-l-ylzirconium 2,3-dimethyl-1,3-butadiene;

diphenylamidoborane-b¡sT |5-inden-l-ylzirconium 2-N, N-dimethylaminobenzyl;

diphenylamidoborane-bis-p5-inden-1 -ylzirconium allyl;

diphenylamidoborane-bis-r |5-inden-1 -ylzirconium η4-1,4-diphenyl-1,3-butadiene;

diphenylamidoborane-bis-r |5-inden-l -ilzirconium p4-2,4-hexadiene;

diphenylamidoborane-bis-T |5-inden-1 -ylzirconium η4-1,4-dinaphthyl-1,3-butadiene; diphenylarynidoborane-bis-r |5-indeii-l-ilzirconium p4-l-phenyl-1,3-pentadiene; diphenylamidoborane-bis-Tf-inden-l-ylzirconium r |4-l, 3-pentadiene, diphenylamidoborane-bis © - (2-methylinden-l-yl) zirconium dichloride; diphenylamidoborane-bis-q5- (2-methylinden-l-yl) zirconium dimethyl; diphenylamidoborane-bis-p bis-dimethylamide5- (2-methylinden-l-yl) zirconium; diphenylainidoborane-bis-Ti5- (2-methylinden-l-yl) zirconium 2-methyl-l, 3-butadiene; diphenylamidoborane-bis-r |5- (2-methylinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene; diphenylainidoborane-bis-Ti5- (2-methylinden-l-yl) zirconium 2-N, N-dimethylamino benzyl; diphenylainidoborane-bis-T]5- (2-methylinden-l-yl) allyl zirconium; diphenylamidoborane-bis-η5- (2-methylinden-l-yl) zirconium η4-1,4- <1ίίβηϊ1-1,3-butadiene; diphenylainidoborane-bis ^5- (2-inetilinden-l-il) circonk ^4-2,4-hexadiene; diphlamidoborane-bis © - (2-methylinden-l-yl) zirconium η4-1.4 <1ΐηαήΐ1-1,3-butadiene;

ES 2 188 235 T3 diphenylamidoborane-bis-n5- (2-methylinden-1-yl) zirconium η4-1-phenyl-1,3-pentadiene; diphenylamidoborane-bis-T}5- (2-methylinden-l-yl) zirconium η4-1,3-pentadiene; diphenylamidoborane-bis dichloride ^5- (2-methyl-4-phenylinden-l-yl) zirconium; diphenylamidoborane-bis-r |5- (2-methyl-4-phenylinden-l-yl) zirconium dimethyl; diphenylamidoborane-bis ^ bis-dimethylamide5- (2-methyl-4-phenylinden-l-yl) zirconium; diphenylamidoborane-bis-r |5- (2-methyl-4-phenylinden-l-yl) zirconium 2-methyl-l, 3-butadiene; diphenylamidoborane-bis-Tf- (2-methyl-4-phenylinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene; diphenylamidoborane-bis-T)5- (2-methyl-4-phenylinden-l-yl) zirconium 2-N, N-dimethylaminobenzyl; diphenylamidoborane-bis-r |5- (2-methyl-4-phenylinden-l-yl) allyl zirconium;

diphenylamidoborane-bis-Ti5- (2-methyl-4-femlinden-l-yl) zirconiumTi4-l>4-diphenyl-1,3-butadiene; diphenylamidoborane-bis-r |5- (2-methyl-4-phenylinden-l-yl) zirconium T |4-2,4-hexadiene; diphenylamidoborane-bis-Ti5- (2-methyl-4-phenylinden-1-yl) zirconium η4-1,4-dinaphthyl-1,3-butadiene; diphenylaniidoborane-bis-Ti5- (2-methyl-4-phenyl] inden-1 -yl) zirconium η4-1-phenyl-1,3-pentadiene; diphenylamidoborane-bis-n5- (2-methyl-4-phenylinden-l-yl) zirconium |4-l, 3-pentadiene; diphenylamidoborane-bis-r dichloride |5- (2-ethyl-4-phenylinden-l-yl) zirconium; diphlamidoborane-bis-Ti5- (2-ethyl-4-phenylinden-l-yl) zirconium dimethyl; diphenylamidoborane-bis - ^ - (2-ethyl-4-phenylinden-l-yl) zirconium bis-dimethylamide; diphenylamidoborane-bis-ri5- (2-ethyl-4-phenylinden-l-yl) zirconium 2-methyl-l, 3-butadiene, diphenylamidoborane-bis-Ti5- (2-ethyl-4-phenylinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene; diphenylamidoborane-bis-r |5- (2-ethyl-4-phenylinden-1-yl) zirconium 2-N, N-dimethylaminobenzyl; diphenylaniidoborane-bis-r |5- (2-ethyl-4- phenylinden-l-yl) allyl zirconium;

diphenylamidoborane-bis-T)5- (2-ethyl-4-phenylinden-l-yl) zirconium i- |4-l, 4-diphenyl-1,3-butadiene; diphenylamidoborane-bis-T |5- (2-ethyl-4-phenilmden-l-yl) zirconium T |4-2,4-hexadiene; diphenylamidoborane-bis-r |5- (2-ethyl-4-phenylinden-l-yl) zirconium η4-1,4-dinaphthyl-1,3-butadiene; diphenylamidoborane-bis-Ti5- (2-ethyl-4-phenylinden-1-yl) zirconium η4-1-phenyl-1,3-pentadiene; diphenylamidoborane-bis-Ti5- (2-ethyl-4-phenylinden-1-yl) zirconium η4-1,3-pentadiene; diphenylamidoborane-bis-r dichloride |5- (2-isopropyl-4-phenylinden-l-yl) zirconium; diphenylamidoborane-bis-T |5- (2-isopropyl-4-femlinden-1-yl) zirconium dimethyl; bis-diphenylamidoborane-bis-r bis-dimethylamide |5- (2-isopropyl-4-phenylinden-l-yl) zirconium; diphenylamidoborane-bis-r |5- (2-isopropyl-4-phenylinden-1-yl) zirconium 2-methyl-1,3-butadiene; diphenylamidoborane-bis-Ti5- (2-isopropyl-4-phenylinden-l-yl) zirconium-2,3-dimethyl-1,3-butadiene; diphenylamidoborane-bis-r |5- (2-isopropyl-4-phenylinden-l-yl) zirconium 2-N, N-dimethylaminobenzyl;

diphenylamidoborane-bis-ri5- (2-isopropyl-4-phenylinden-l-yl) allyl zirconium; diphenylamidoborane-bis-r |S- (2-isopropyl-4-phenylinden-l-yl) zirconium r |4-l, 4-diphenyl-1,3-butadiene;

diphenylamidoborane-bis-Ti5- (2-isopropyl-4-phenylinden-l-yl) zirconium r |4-2,4-hexadiene; diphenylamidoborane-bis-h5- (2-isopropyl-4-phenylinden-l-yl) zirconium q4-l, 4-dinaphthyl-l, 3-butadiene;

diphenylaniidoborane-bis-T]5- (2-isopropyl-4-phenylinden-l-yl) zirconium Tj4-l-phenyl-1,3-pentadiene; diphenylamidoborane-bis-hs- (2-isopropyl-4-phenylinden-l-yl) zirconium r |4-l, 3-pentadiene; dipheni] amidoborane-bis-r dichloride |5- (2-methyl-4-naphthylinden-l-yl) zirconium;

ES 2 188 235 T3 diphenylamidoborane-bis-T |5- (2-methyl-4-naphthylinden-l-yl) zirconium dimethyl; diphenylamidoborane-bis-η bis-dimethylamide5- (2-methyl-4-naphthylinden-l-yl) zirconium; diphenylamidoborane-bis-r |5- (2-Inethyl-4-naphthylinden-1-yl) zirconium 2-methyl-1,3-butadiene; diphenylamidoborane-bis-η5- (2-methyl-4-naphthylinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene; diphenylamidoborane-bis © - (2-methyl-4-naphthylinden-l-yl) zirconium 2-N, N-dimethylaminobenzyl; diphlamidoborane-bis-r |5- (2-methyl-4-naphthylinden-1-yl) allyl zirconium;

diphenylamidoborane-bis-N5- (2-methyl-4-naphthylinden-1-yl) zirconium η4-1,4-diphenyl-1,3-butadiene; diphenylamidoborane-bis-Ti5- (2-methyl-4-naphthylinden-l-yl) zirconium r |4-2,4-hexadiene; diphenylamidoborane-bis-T |5- (2-methyl-4-naphthylinden-1-yl) zirconium η4-1,4-dinaphthyl-1,3-butadiene; diphenylamidoborane-bis-η5- (2-methyl -4-naphthylinden-1 -yl) zirconium η4-1-phenyl-1,3-pentadiene; diphenylaniidoborane-bis-Ti5- (2-methyl-4-naphthylinden-l-yl) zirconium r |4-l, 3-pentadiene; diphenylamidoborane-bis © - (2-methyl-4-bis (3,5-trifluoromethyl) phenylinden-lyl) zirconium dichloride;

diphenylamidoborane-bis-r |5- (2-methyl-4-bis (3,5-trifluoroinethyl) phenylinden-l-yl) zirconium dimethyl; diphenylamidoborane-bis-n bis-dimethylamides- (2-methyl-4-bis (3,5-trifluoromethyl) phenylindenl-yl) zirconium;

diphenylamidoborane-bis-r |5- (2-methyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium 2-methyl1,3-butadiene;

diphenylamidoborane-bis-ri5- (2-methyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene;

diphenylamidoborane-bis-n5- (2-methyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium 2-N, N-dimethylaminobenzyl;

diphenylamidoborane-bis-T |5- (2-Inethyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) allyl zirconium; dimethylamidoborane-bis-r |5- (2-methyl-4-bis (3,5-trifluoromethyl) femlinden-l-yl) zirconium η4-1,4-diphenyl-1,3-butadiene;

dimethylamidoborane-bis-ri5- (2-methyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium η4-2.4hexadiene;

dimethylamidoborane-bis-r |5- (2-methyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium η4-1,4dinaphthyl-1,3-butadiene;

dimethylamidoborane-bis-Ti5- (2-methyl-4-bis (3,5-trifluoromethyl) phenylinden-1-yl) zirconium η4-1-phenyl-1,3-pentadiene;

dimethylamidoborane-bis-T |5- (2-Inethyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium η4-1.3 pentadiene;

diphenylamidoborane-bis-r dichloride |5- (2-ethyl-4-bis (3,5-trifluoromethyl) phenylinden-lyl) zirconium;

diphenylamidoborane-bis-N5- (2-ethyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium dimethyl; bis-dimethylamide of difchnylamidoborane-bis ^s- (2-ethyl-4-bis (3,5-trifluoromethyl) phenylinden-lyl) zirconium;

diphenylamidoborane-bis-Ti5- (2-ethyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium 2-methyl1,3-butadiene;

diphenylamidoborane-bis-r |5- (2-ethyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene;

ES 2 188 235 T3 diphenylamidoborane-bis-T}5- (2-ethyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium 2-N, N-dimethyl aminobenzyl;

diphenylamidoborane-bis-Tf- (2-ethyl-4-bis (3,5-trifluoromethyl) phenylinden-1-yl) zirconium allyl; diinethylamidoborane-bis-Ti5- (2-ethyl-4-bis (3,5-trifluoromethyl) phenylinden-1-yl) zirconium η4-1,4-diphenyl-1,3-butadiene;

dimethylamidoborane-bis-r |5- (2-ethyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium η4-2.4hexadiene;

dimethylamidoborane-bis-r |5- (2-ethyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium4-l, 4-dinaphthyl-1,3-butadiene;

dimethylamidoborane-bis-r |5- (2-ethyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconior |4-l-phenyl1.3-pentadiene;

dimctylamidoborane-bis ^5- (2-ethyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium η4-1,3pentadiene;

dipheni1amidoborane-bis-T dichloride |5- (2-isopropyl-4-bis (3,5-trinuoromethyl) phenylinden-lyl) zirconium;

diphenylamidoborane-bis-T |5- (2-isopropyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium dimethyl;

bis-diphenylamidoborane-bis-r bis-dimethylamide |5- (2-isopropyl-4-bis (3,5-trifluoromethyl) phenylinden-1-yl) zirconium;

diphenylamidoborane-bis-T)5- (2-isopropyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium 2-methyl-1,3-butadiene;

diphenylamidoborane-bis-TV- (2-isopropyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene;

diphenylamidoborane-bis-ti5- (2-isopropyl-4-bis (3,5-trifluoromethyl) phenylinden-l-iI) 2N zirconium, N-dimethylaminobenzyl;

diphenylamidoborane-bis-q5- (2-isopropyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) allyl zirconium; dimethylamidoborane-bis-r |5- (2-isopropyl-4-bis (3,5-trifluoromethyl) fcnilinden-l-yl) zirconium η41.4- diphenyl-l, 3-butadiene, dimethylamidoborane-bis-T |5- (2-isopropyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium η42.4- hexadiene;

dimethylamidoborane-bis-T |5- (2-isopropyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium η41,4-dinaphthyl-1,3-butadiene;

dimethylamidoborane-bis-T |5- (2-isopropyl-4-bis (3,5-trii] uoromethyl) phenylinden-l-yl) zircomo η41-phenyl-1,3-pentadiene;

dimethylamidoborane-bis-Ti5- (2-isopropyl-4-bis (3,5-trifluoromethyl) phenylinden-1-yl) zirconium η41,3-pentadiene;

diphemlamidoborane-bis dichloride ^5- (3-isopropylinden-l-yl) zirconium; diphenylamidoborane-bis-Ti5- {3-isopropylinden-l-yl) zirconium dimethyl; bis-diphenylamidoborane-bis-T bis-dimethylamide |5- (3-isopropylinden-li]) zirconium; diphenylamidoborane-bis-Ti5- (3-isopropylinden-1-yl) zirconium 2-methyl-1,3-butadiene; dipheni] amidoborane-bis-T |5- (3-isopropylinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene; diphenylamidoborane-bis-Ti5- (3-isopropylinden-l-yl) zirconium 2-N, N-dimethylaminobenzyl; diphenylamidoborane-bis-r |5- (3-isopropylinden-1-yl) allyl zirconium;

ES 2 188 235 T3 diphenylamidoborane-bis-q5- (3-isopropylinden-l-yl) zirconium r |4-l, 4-diphenyl-1,3-butadiene; diphenylamidoborane-bis-r |5- (3-isopropylinden-l-yl) zirconium T |4-2,4-hexadiene; diphenylamidoborane-bis-r |5- (3-isopropylinden-l-yl) zircomo η4-1,4- (ϋηΗ & ί1-1,3- ^ ΐ3 <1ίεηο; diphenylamidoborane-bis-p5- (3-isopropylinden-l-yl) zirconium ri4-l-phenyl-1,3-pentadiene; diphenylamidoborane-bis-η5- (3-isopropylinden-l-yl) zirconium q4-l, 3-pentadiene; diphenylamidoborane-bis-q dichloride5- (3-t-butylinden-l-yl) zirconium; diphenylamidoborane-bis-p5- (3-t-butylinden-l-yl) zirconium dimethyl; bis-diphenylamidoborane-bis-r bis-dimethylamide |5- (3-t-butylinden-l-yl) zirconium; diphenylamidoborane-bis © - (3-t-butylinden-l-yl) zirconium 2-methyl-1,3-butadiene; diphenylamidoborane-bis-p5- (3-t-butylinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene; diphenylamidoborane-bis-r |5- (3-t-butylmden-1-yl) zircomo 2-N, N-dimethylaminobenzyl; diphenylamidoborane-bis-η5 - (3-t-Butylinden-1-ylzirconium allyl;

diphenylamidoborane-bis-Ti5- (3-t-butylinden-l-yl) zirconiumTi4-l, 4-diphenyl-l>3-butadiene; difchnylamidoborane-bis-T |5- (3-t-butylinden-l-yl) zirconium T |4-2,4-hexadiene; diphenylamidoborane-bis-Ti5- (3-t-butylinden-l-yl) zirconium η4-1,4-dinaphthyl-1,3-butadiene; diphenylamidoborane-bis-h5- (3-t-butylinden-1 -yl) zirconium η4-1-phenyl-1,3-pentadiene; d¡phenylam¡doborano-bis-ry5- (3-t-butylinden-l-yl) zirconium q4-l, 3-pentadiene; bis (trimethylsilyl) amidoborane-bis-T dichloride |s-cyclopentadienylzirconium; bis (trimethylsilyl) amidoborane-bis ^ '- cyclopentadienylzirconium dimethyl; bis-dimethylamide of b¡s (trimethylsilyl) amidoborane-bis-T |5-cyclopentadiemlzirconium; bis (trimethylsilyl) amidoborane-bis-Ti5-cyclopentadienylzirconium 2-methyl-1,3-butadiene; bis (trimethylsilyl) amidoborane-bis-T |5-cyclopentadienylzirconium 2,3-dimethyl-1,3-butadiene; bis (trimethylsilyl) amidoborane-bis-T |5-cyclopentadienylzirconium 2-N, N-dimethylaminobenzyl; bis (trimctylsilyl) amidoborane-bis-Ty-cyclopentadienylzirconium allyl; bis (trimethylsilyl) amidoborane-bis-T,5-cyclopentadienylzirconium η4- 1,4-diphenyl-1,3-butadiene; bis (trimethylsilyl) amidoborane-bis-r |5-cyclopentadienylzirconium n4-2,4-hexadiene; bis (trimethylsilyl) ainidoborane-bis-r |5-cyclopentadienylcircomo r |4-l, 4-dinaphthyl-l, 3-butadiene; bis (trimethylsilyl) amidoborane-bis-q5-cyclopentadienylzirconium η4-1-phenyl-1,3-pentadiene; bis (trimethylsilyl) amidoborane-bis-r |5-cyclopentadienylzirconiumTi4-l, 3-pentadicne; bis (trimethylsilyl) amidoborane-bis-q dichloride5-inden-l-ilzirconium; bis (trimethylsilyl) amidoborane-bis-r |5-inden-l-ylzirconium dimethyl; bis (trimethylsilyl) amidoborane-bis-q bis-dimethylamide5-inden-l-ilzirconium; bis (trimethylsilyl) amidoborane-bis-r |5-inden-l-ylzirconium 2-methyl-1,3-butadiene; bis (tnmethylsilyl) airudoborane-bis-r |5-inden-l-ylzircone2,3-dimethyl-b3-butadiene, bis (trimethylsilyl) amidoborane-bis ^5-inden-l-ylzirconium 2-N, N-dimethylaminobenzyl; bis (trimethylsilyl) amidoborane-bis © -inden-l-ylzirconium allyl; bis (trimethylsilyl) amidoborane-bis-r |5-inden-l-ilzirconium r |4-l, 4-diphenyl-1,3-butadiene; bis (trimethylsilyl) amidoborane-bis-Ti5-inden-l-ilzirconiumTi4-2,4-hexadiene; bis (trimethylsilyl) amidoborane-bis-Ti5-inden-l-ilcirconior |4-l, 4-dinaphthyl-l, 3-butadiene; bis (trimethylsili,) amidoborane-bis ^5-inden-1 -ylzirconium η4-1-phenyl-1,3-pentadiene; bis (trimethylsilyl) amidoborane-bis-r |5-inden-l-ilzirconium r |4-l, 3-pentadiene; bis (trimethylsilyl) amidoborane-bis-r dichloride |5- (2-methylinden-l-yl) zirconium;

ES 2 188 235 T3 bis (trimeulsilyl) aimdoborane-bis- © (2-methylinden-l-yl) zirconium dimethyl; bis (trimethylsilyl) amidoborane-bis-Ti bis-dimethylamide5- (2-methylinden-l-yl) zirconium; bis (trimethylsilyl) amidoborane-bis-Ti5- (2-methylinden-l-yl) zirconium 2-methyl-l, 3-butadiene; bIS (trimethylsilyl) amidoborane-bis-T |5- (2-methylinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene; bis (trimethylsilyl) amidoborane-bis-r |5- (2-Methylinden-l-yl) zirconium 2-N, N-dimethylaminobenzyl; bis (trimethylsilyl) amid <Aorano-bis ^,- (2-Methylinden-1 -ylzirconium allyl;

bis (trinyethylsilyl) amidoborane-bis-Ti5- (2-methylinden-l-yl) zirconium η4-1,4-diphenyl-1,3-butadiene; bis (trimethylsilyl) amidoborane-bis-r |5- (2-methylinden-l-yl) zirconium r |4-2,4-hexadiene; bis (trimethylsilU) amidoborane-bis-Tj5- (2-inetilinden-l-il) zircon¡OTi4-l, 4-dmaphthyl-l, 3-butadiene; bis (trimethylsilyl) amidoborane-bis-r |5- (2-methylinden-l-yl) zirconium q4-l-phenyl-1,3-pentadiene; bis (trimethylsilyl) amidoborane-bis-r |5- (2-methylinden-l-yl) zirconium i- |4-l, 3-pentadiene; bis (trimethylsilyl) amidoborane-bis-Ti dichloride5- (2-methyl-4-phenylinden-l-yl) zircom; bis (trimethylsilyl) amidoborane-bis-Ti5- (2-methyl-4-phenylinden-l-yl) zirconium dimethyl; bis (trimethylsilyl) amidoborane-bis ^ bis-dimethylamide5- (2-methyl-4-phenylinden-l-yl) zirconium; bis (trimethylsilyl) amidoborane-bis-T |5- (2-methyl-4-phenylinden-l-yl) zircomo 2-methyl-l, 3-butadiene;

bis (tnmethylsilyl) amidoborane-bis ^5- (2-methyl-4-phenylinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene;

bis (trimethylsilyl) amidoborane-bis-r |5- (2-methy] -4-phenylinden-l-yl) zirconium2-N, N-diinethylaminobenzyl;

bis (trimethylsilyl) amidoborane-bis-q5- (2-methyl-4-femlinden-l-yl) allyl zirconium; bis (trimethylsilyl) amidoborane-bis-T)5- (2-methyl-4-phenylinden-l-yl) zirconium r |4-l, 4-diphenyl-1,3-butadiene;

bis (trimethylsilyl) amidoborane-bis-r |5- (2-methyl-4-phenylinden-l-yl) zirconium r |4-2,4-hexadiene; bis (triraethylsilyl) amidoborane-bis-Tf- (2-methyl-4-phenylinden-l-yl) zirconium T,4-l, 4-dinafyl-l, 3-butadiene;

bis (trimethylsilyl) amidoborane-bis-Ti5- (2-methyl-4-phenylinden-1-yl) zirconium η4-1-phenyl-1,3-pentadiene;

bis (trimethylsilyl) amidoborane-bis-Ti5- (2-methyl-4-phenylinden-1-yl) zirconium η4-1,3-pentadiene; bis (trimethylsilyl) amidoborane-bis-ri dichloride5- (2-methyl-4-naphthylinden-l-yl) zirconium; bis (trimethylsilyl) ainidoborane-bis-Ti5- (2-methyl-4-naphthylinden-1 -yl) zirconium dimethyl; bis (trimethylsilyl) amidoborane-bis-r bis-dimethylamide |5- (2-methyl-4-naphthylinden-l-yl) zircom; bis (trimctylsilyl) amidoborane-b¡sr |5- (2-methyl-4-naphthylinden-l-yl) zirconium 2-methyl-l, 3-butadiene; 'bis (trimethylsilyl) amidoborane-bis-T |5- (2-methiI-4-naphthylinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene;

bis (trimethylsilyl) amidoborane-bis-Ti5- (2-methyl-4-naphthylinden-l-yl) zirconium 2-N, N-dimethylaminobenzyl;

bis (trimethylsilyl) amidoborane-bis ^5- (2-methyl-4-naphthylinden-l-yl) allyl zirconium; bis (trimethylsilyl) amidoborane-bis-Ti5- (2-methyl-4-naphthylinden-l-yl) zirconium r |4-l, 4-diphenyl-1,3-butadiene;

bis (trimethylsilyl) amidoborane-bis-Ti5- (2-methyl-4-naphthylinden-l-yl) zirconium r |4-2,4-hexadiene;

ES 2 188 235 T3 bis (trimethylsilyl) amidoborane-bis © - (2-methyl-4-naphthylinden-l-yl) zirconium ^ -l, 4-dinaphthyl-l, 3-butadiene;

bis (trimethylsilyl) amidoborane-bis-T |5- (2-methyl-4-naphthylinden-1-yl) zirconium η4-1-phenyl-1,3-pentadiene;

bis (trimethylsilyl) ainidoborane-bis-T |5- (2-methyl-4-naphthylinden-l-yl) zirconium r |4-l, 3-pentadiene; bis (trimethylsilyl) aniidoborane-bis dichloride ^5- (3-isopropylinden-l-yl) zircom; bis (trimethylsilyl) amidoborane-bis-T |5- (3-isopropylinden-l-yl) zirconium dimethyl; bis (trimethylsilyl) amidoborane-bis-T bis-dimethylamide)5- (3-isopropylinden-l-yl) zirconium; bis (triinethylsilyl) aimdoborane-bis-Ti5- (3-isopropylinden-1-yl) zirconium 2-methyl-1,3-butadiene; bis (trimethylsilyl) amidoborane-bis-ri5- (3-isopropylinden-l-yl) zirconium 2,3-dimethyl-1,3-butadiene;

bis (trimethyl] silyl) amidoborane-bis-r |5- (3-isopropylinden-l-yl) zircomo 2-N, N-dimethylaminobenzyl;

bis (trimethylsilyl) amidoborane-bis © - (3-isopropylinden-l-iI) allyl zirconium; bis (tnmethylsilyl) amidoborane-bis-r |5- (3-isopropylinden-1-yl) zirconium η4-1,4-diphenyl-1,3-butadiene;

bis (trimethylsilyl) amidoborane-bis-r |5- (3-¡sopropylinden-l-yl) zirconium r |4-2,4-hexadiene; bis (trimethylsilyl) amidoborane-bis-Ti5- (3-isopropylinden-1-yl) zirconium η4-1,4-dinaphthyl-1,3-butadiene;

bis (trimethylsilyl) aniidoborane-bis-Tf- (3-isopropylinden-1-yl) zirconium η4-1-phenyl-1,3-pentadiene;

bis (triinethylsilyl) amidoborane-bis-Ti5- (3-isopropylinden-l-yl) zirconium η4-1,3-pentadiene; bis (trimethylsilyl) amidoborane-bis-r dichloride |5- (3-t-butylinden-l-yl) zirconium; bis (trimethylsilyl) amidoborane-bis-r |5- (3-t-butylinden-l-yl) zirconium dimethyl; bis (trimethylsilyl) amidoborane-bis ^ bis-dimethylamide5- (3-t-butylinden-l-yl) zirconium; bis (trimethylsilyl) amidoborane-bis-r |5- (3-t-butylinden-l-yl) zirconium 2-methyl-l, 3-butadiene; bis (trimethylsilyl) amidoborane-bis-T |5- (3-t-Butylinden-1-yl) zirconium 2,3-dimethyl-1,3-butadiene; bis (trimethylsilyl) amidoborane-bis-Ti5- (3-t-butylinden-l-yl) zirconium 2-N, N-dimethylaminobenzyl; bis (trimethylsilyl) amidoborane-bis ^5- (3-t-Butylinden-1-yl) allyl zirconium; bis (trimethylsilyl) amidoborane-bis-T |5- (3-t-butylinden-l-yl) zirconium r |4-l, 4-diphenyl-1,3-butadiene;

bis (trimethylsilyl) amidoborane-bis-T |5- (3-t-butylinden-l-yl) zirconium r |4-2,4-hexadiene; bis (trimethylsilyl) amidoborane-bis-r |5- (3-t-butylinden-l-yl) c¡rcon¡o η4-1,4-άίη3ήϋ-1,3-butadiene;

bis (trimethylsilyl) amidoborane-bis-Ti5- (3-t-butylinden-l-yl) zirconium T)4-l-phenyl-1,3-pentadiene; bis (trimethylsilyl) amidoborane-bis-Ti5- (3-t-butylinden-l-yl) zirconium r |4-l, 3-pentadiene; bis (diisopropylamido) diborane-1,2-bis-r dichloride5- (2-methyl-4-fcmlmden-l-yl) zirconium; bis (diisopropylamido) diborane-1,2-bis-r |5- (2-Niethyl-4-phenylinden-1-yl) zirconium dimethyl;

bis (diisopropylaniido) diborane-1,2-bis-η bis-dimethylamide 5- (2-methyl-4-phenylinden-1 yl) zirconium;

bis (diisopropylamido) diborane-1,2-bis © - {2-methyl-4-phenylinden-l-yl) zirconium 2-methyl-1,3-butadiene;

ES 2 188 235 T3 bis (diisopropylamido) diborane-1,2-bis-Ti5- (2-methyl-4-phenylinden-l-yl) zircomo 2,3-dimethyl-1,3-butadiene;

bis (diisopropylamido) diborane-1,2-bis-T |5- (2-Inethyl-4-phenylinden-l-yl) zirconium 2-N, N-dimethylaminobcnzyl;

bis (diisopropylainido) diborane-1,2-bis-n5- (2-methyl-4-phenylinden-1-yl) allyl zirconium; bis (diisopropylamido) diborane-1,2-bis-n5- (2-methyl-4-phenylinden-l-yl) circoiuo η4-1,4-diphenyl1,3-butadiene;

bis (diisopropylamido) diborane-1,2-bis-Ti5- (2-inethyl-4-phenyl] inden-l-yl) circomo r |4-2,4-hexadiene;

bis (diisopropylamido) diborane-1,2-bis-Ti5- (2-methyl-4-phenylinden-1-yl) zirconium η4-1,4-dinaphthyl1,3-butadiene;

bis (diisopropylamido) diborane-1,2-bis ^5- (2-methyl-4-phenylinden-1-yl) zirconium η4-1-phenyl-1,3pentadiene;

bis (diisopropylamido) diborane-1,2-bis-T |5- (2-methyl-4-phenylinden-1-yl) zirconium η4-1,3-pentadiene;

dimethylaniidoborane-bis-r dichloride |5-cyclopentadienyl hafnium; dimethylamidoborane-bis-T]5-cyclopentadienyl hafnium dimethyl; bis-dimethylamidoborane-bis-r bis-dimethylamide |s-cyclopentadieiiyl hafnium; dimethylamidoborane-bis-T |5-cyclopentadienyl hafnium 2-methyl-1,3-butadiene; dimethylamidoborane-bis-T ^ -cyclopentadienyl hafnium 2,3-dimethyl-1,3-butadiene; dimethylamidoborane-bis-r |5-cyclopentadienyl hafnium 2-N, N-dimethylaminobenzyl; dimethylamidoborane-bis-Ti'-cyclopentadienyl hafnium allyl; dimethylamidoborane-bis-r |5-cyclopentadieml hafnium ri4-l, 4-diphenyl-1,3-butadiene; dimethylamidoborane-bis-Ti5-cyclopentadienyl hafnium r |4-2,4-hexadiene; dimethylamidoborane-bis-T)5-cyclopentadienyl hafnium T |4-l, 4-dinaphthyl-l, 3-butadiene; dimethylamidoborane-bis-T ^ -cyclopentadienyl hafnium T |4-l-phenyl-1,3-pentadicne; dimethylamidoborane-bis-Ti5-cyclopentadienyl hafnium T)S-l, 3-pentadiene; dimethylamidoborane-bis-r dichloride)s-n-butylcyclopentadienyl hafnium; dimethylamidoborane-bis-r |s-n-butylcyclopentadienyl hafnium dimethyl; dimethylamidoborane-bis-T ^ -n-butylcyclopentadienyl hafnium bis-dimethylamide; dimethylamidoborane-bis-Ti5-n-butylcyclopentadieni] hafnium 2-methyl-1,3-butadiene; dimethylamidoborane-bis-Tf-n-butylcyclopentadienyl hafnium 2,3-dimethyl-1,3-butadiene; dimethylamidoborane-bis-Ti5-n-butylcyclopentadieiiyl hafnium 2-N, N-dimethylaminobenzyl; dimethylamidoborane-bis-T |5-n-butylcyclopentadienyl hafnium allyl;

dimethylamidoborane-bis-r |5-n-butylcyclopentadienyl hafnium Ti4-l, 4-diphenyl-1,3-butadiene; dimethylamidoborane-bis-r ^ -n-butylcyclopentadienyl hafnium r |4-2,4-hexadiene; dimethylamidoborane-bis-T |5-n-butylcyclopentadieml hafnium r |4-l, 4-dinaphthyl-l, 3-butadiene; dimethylamidoborane-bis-r |5-n-butylcyclopentadieml hafnium Ti4-l-phenyl-1,3-pentadiene; dimethylamidoborane-bis-Ti5-n-butylcyclopentadieml hafnium r |5-l, 3-pentadiene; dimethylamidoborane-bis-T dichloride |5-inden-l-ilhafnium;

dimethylamidoborane-bis-n5-inden-l-ylhafnium dimethyl; dimethylamidoborane-bis-r ^ -inden-l-ylhafnium bis-dimethylamide;

ES 2 188 235 T3 dimeülanúdoborano-bis-r |5-inden-1 -ilhafnium 2-methyl-1,3-butadiene;

dimethylamidoborane-bis-T |5-inden-1 -ilhafnium 2,3-dimethyl-1,3-butadiene;

dimethylamidoborane-bis-T |5-inden-1 -ilhafnium 2-N, N-dimethylaminobenzyl;

dimctylamidoborane-bis-r |5-inden-l-ylhafnium allyl;

dimethylamidoborane-bis-T |5-inden-1 -ilhafnium η4-1,4-diphenyl-1,3-butadiene;

dimethylamidoborane-bis-if-inden-l-ylhafnium r |4-2,4-hexadiene;

dimethylamidoborane-bis-T)5-inden-l -ilhafnium η4-1,4-dinaphthyl-1,3-butadiene;

dimethylamidoborane-bis-r |5-inden-1 -ilhafnium η4-1-phenyl-1,3-pentadiene;

dimethylamidoborane-bis-r |5-inden-l -ilhafnium η4-1,3-pentadiene;

dimethylamidoborane-bis-p dichloride5- (2-methylinden-l-yl) hafnium, dimethylamidoborane-bis-p5- (2-methylinden-l-yl) hafhio dimethyl;

Dimethylamidoborane-bis-q bis-dimethylamide5- (2-methylinden-l-yl) hafnium;

dimethylamidoborane-bis-T |5- (2-methylinden-1-yl) hafnium 2-methyl-1,3-butadiene;

dimethylamidoborane-bis-p5- (2-methylinden-l-yl) hafnium 2,3-dimethyl-1,3-butadiene; dimethylamidoborane-bis-r |5- (2-methylinden-l-yl) hafTiio 2-N, N-dimethylaminobenzyl; dimethylamidoborane-bis-r |5- (2-methylinden-l-yl) hafmo allyl;

dimethylamidoborane-bis-r |5- (2-methylinden-l-yl) hafnior |4-l)4-diphenyl-1,3-butadiene; dimethylamidoborane-bis-Ti5- (2-methylinden-l-yl) hafnium ri4-2,4-hexadiene; dimethylamidoborane-bis-T |5- (2-methylinden-l-yl) hafnior |4-l, 4-dinaphthyl-l, 3-butadiene; dimethylamidoborane-bis-r |5- (2-methylinden-1 -yl) hafnium η4-1-phenyl-1,3-pentadiene; dimethylamidoborane-bis-T |5- (2-methylinden-l-yl) hafnium T |4-l, 3-pentadiene; dimethylamidoborane-bis-p dichloride5- (2-methyl-4-phenylinden-l-yl) hafnium; dimethyl amidoborane-bis-r |5- (2-methyl-4-phenylinden-l-yl) hafnium dimethyl; Dimethylaimdoborane-bis-r bis-dimethylamide |5- (2-methyl-4-phenylinden-l-yl) hafnium; dimethylamidoborane-bis-q5- (2-melyl-4-phenylinden-l-yl) hafnium 2-methyl-l, 3-butadiene; dimethylamidoborane-bis-ps- (2-methyl-4-phenylinden-l-yl) hafhio 2,3-dimethyl-1,3-butadiene; dimethylamidoborane-bis-r |5- (2-methyl-4-phenylindcn-l-yl) hafnium 2-N, N-dimethylaminobenzyl; dimethylamidoborane-bis-T |5- (2-methyl-4-phenylinden-l-yl) hafnium allyl; dimethylamidoborane-bis-ii5- (2-methyl-4-phenylinden-l-yl) hafhioT |4-l, 4-diphenyl-1,3-butadiene; dinyethylamidoborane-bis-p5- (2-methyl-4-phenylinden-l-yl) hafnium iq4-2,4-hexadiene; dimethylamidoborane-bis-p5- (2-methyl-4-phenylinden-l-yl) hafnium p4-l, 4-dinaphthyl-l, 3-butadiene; dimethylamidoborane-bis-p5- (2-methyl-4-phenylinden-1 -yl) hafnium η4-1-phenyl-1,3-pentadiene; dimethylamidoborane-bis-q5- (2-methyl-4-phenylinden-l-yl) hafnium p4-l, 3-pentadiene; dimethylamidoborane-bis-q dichloride5- (2-methyl-4-naphthylinden-l-yl) hafhio; dimethylamidoborane-bis-T |5- (2-Inethyl-4-naphthylinden-1-yl) hafnium dimethyl; Dimethylamidoborane-bis-p bis-dimethylamide5- (2-methyl-4-naphthylinden-l-yl) hafnium; dimethylamidoborane-bis-T |5- (2-methyl-4-naphthylinden-l-yl) hafnium 2-methyl-l, 3-butadiene; dimethylamidoborane-bis-p5- (2-methyl-4-naphthylinden-l-yl) hafhio 2,3-dimethyl-1,3-butadiene; dimethylamidoborane-bis-T |5- (2-methyl-4-naphthylinden-l-yl) hafnium 2-N, N-dimethylaminobenzyl; dimethylamdoborane-bis-T |5- (2-methyl-4-naphthylinden-l-yl) hafhio allyl; dimethylamidoborane-bis-Ti5- (2-methyl-4-naphthylindcn-l-yl) hafhio r |4-l, 4-diphenyl-1,3-butadiene; dimethylamidoborane-bis-T |S- (2-methyl-4-naphthylinden-l-yl) hafnium r |4-2,4-hexadiene;

ES 2 188 235 T3 dimethylamidoborane-bis-Tf- (2-methyl-4-naphthylinden-l-yl) hafnium T |4-l, 4-dinaphthyl-l, 3-butadiene; dimethylamidoborane-bis ^5- (2-methyl-4-naphthylinden-l-yl) hafnium η4-1-phenyl-1,3-pentadiene; dimethylamidoborane-bis-ri5- (2-methyl-4-naphthylinden-1 -yl) hafhio η4-1,3-pentadiene; dimethylamidoborane-bis © - (3-isopropylinden-l-yl) hafmo dichloride;

dimethylainidoborane-bis-Ti5- (3-isopropylinden-l-yl) hafnium dimethyl;

dimethylamidoborane-bis® - (3-isopropylinden-l-yl) hafnium bis-dimethylamide; dimethylamidoborane-bis © - (3-isopropylinden-1-yl) hafnium 2-methyl-1,3-butadiene; dimethyl amidoborane-bis-T)5- (3-isopropylinden-1-yl) hafiño 2,3-dimethyl-1,3-butadiene; dimethylamidoborane-bis-r |5- (3-isopropylinden-1-Il) hafnium 2-N, N-dimethylaminobenzyl; dimethylamidoborane-bis © - (3-isopropylinden-1-yl) hafiiio allyl;

dimethylamidoborane-bis-r |5- (3-isopropylinden-l-yl) hafhio Ti4-l, 4-diphenyl-1,3-butadiene; dimethylamidoborane-bis-Ti5- (3-isopropylinden-l-yl) hafhioii4-2,4-hexadiene; dimethylamidoborane-bis-r |5- (3-isopropylinden-1 -yl) hafnium η4-1,4-dinaphthyl-1,3-butadiene; dimethylamidoborane-bis-r |5- (3-isopropylinden-1 -yl) hafnium η4-1-phenyl-1,3-pentadiene; dimethylamidoborane-bis-η5- (3-isopropylinden-1 -yl) hafnium η4-1,3-pentadiene; dimethylamidoborane-bis © - (3-t-butylinden-l-yl) hafnium dichloride; dimethylamidoborane-bis-r |5- (3-t-butylinden-l-yl) hafhio dimethyl; dimethylamidoborane-bis © - (3-t-butylinden-l-yl) hafnium bis-dimethylamide; dimethylamidoborane-bis-r |5- (3-t-butylinden-l-yl) hafhio2-methyl-l, 3-butadiene; dimethylamidoborane-bis-η5- (3-t-Butylinden-1-yl) hafnium 2,3-dimethyl-1,3-butadiene; dimethylamidoborane-bis-n5- (3-t-butylinden-l-yl) hafhio 2-N, N-dimethylaminobenzyl; dimethylamidoborane-bis ^5- (3-t-Butylinden-1-yl) hafnium allyl;

dimethylamidoborane-bis-η 5- (3-t-butylinden-1 -yl) hafnium η4-1,4-diphenyl-1,3-butadiene; dimethylamidoborane-bis ^5- (3-t-butylinden-l-yl) liafnM ^4-2,4-hexadiene; dimethylamidoborane-bis-η5- (3-t-butylinden-1 -yl) hafnium η4-1,4-dinaphthyl-1,3-butadiene; dimethylamidoborane-bis-ηs- (3-t-butylinden-1 -yl) hafnium η4-1-phenyl-1,3-pentadiene; dimethylamidoborane-bis-η5- (3-t-butylinden-l -iljhafnium η4-1,3-pentadiene; diisopropylamidoborane-bis © -cyclopentadienylhafnium dichloride; diisopropylamidoborane-bis © -cyclopentadienylhafhio dimethyl; diisopropylamidoborane-bis © -cyclopentadienylhafnium bis-dimethylamide; diisopropylamidoborane-bis © -cyclopentadinenylhafnium 2-methyl-1,3-butadiene; diisopropylamidoborane-bis © -cyclopentadienylhafhio 2,3-dimethyl-1,3-butadiene; diisopropylamidoborane-bis © -cyclopentadienylhafhio 2-N, N-dimethylaminobenzyl; diisopropylamidoborane-bis ^5-cyclopentadienylhafhio allyl; diisopropylamidoborane-bis © -cyclopentadienylhafhio η4-1,4-diphenyl-1,3-butadiene; diisopropylamidoborane-bis © -cyclopentadiemlhafnium η4-2.4 ^ βχ3 (1ίβηο; diisopropylamidoborane-bis © -cyclopentadienylhafhio η4-1,4-dinaphthyl-1,3-butadiene; diisopropylamidoborane-bis © -cyclopentadienylhafnium η4-1-phenyl-1,3-pentadiene; diisopropylamidoborane-bis © -cyclopentadienylhafnium η5-1,3-pentadiene; diisopropylamidoborane-bis dichloride ^5-inden-l-ilhafiiio; diisopropylamidoborane-bis ^5-inden-l-ylhafino dimethyl;

Diisopropylamidoborane-bis-n bis-dimethylamide5-inden-l-ilhafnium;

ES 2 188 235 T3 diisopropylamidoborane-bis-r |5-inden-1 -ilhafnium 2-methyl-1,3-butadiene; diisopropylamidoborane-bis-T |5-inden-l-ylhafriio 2,3-dimethyl-1,3-butadiene; diisopropylamidoborane-bis-n5-inden-l-ylhafnium 2-N, N-dimethylaminobenzyl; diisopropylamidoborane-bis-r |5-inden-1 -ilhafnium allyl;

diisopropylamidoborane-bis-Tf-inden-l-ylhatnio T / -l, 4-diphenyl-l, 3-butadiene; diisopropylamidoborane-bis-u5-inden-1-ylhafnium T |4-2,4-hexadiene; diisopropylamidoborane-bis-r |5-indcn-1 -ilhafnium η4-1,4-dinaphthyl-1,3-butadiene; diisopropylamidoborane-bis-Tf-inden-1-ylhafnium η4- 1-phenyl-1,3-pentadiene; dnsopropylamidoborane-bis-r |5-inden-l -ilhafnium T |4-l, 3-pentadiene; diisopropylamidoborane-bis-ti dichloride5- (2-methylinden-l-yl) hafnium; diisopropylamidoborane-bis-u5- (2-methylinden-l-yl) hafnium dimethyl; bis-diisopropylamidoborane-bis-r bis-dimethylamide |S- (2-methylinden-l-yl) hafnium; diisopropylamidoborane-bis-ri5- (2-methylinden-l-yl) hafhio 2-methyl-l, 3-butadiene; diisopropylamidoborane-bis-T |5- (2-methylinden-1-yl) hafnium 2,3-dimethyl-1,3-butadiene; diisopropylamidoborane-bis-r |5- (2-methylinden-l-yl) hafnium 2-N, N-dimethylaminobenzyl; diisopropylamidoborane-bis-us- (2-methylinden-1-yl) hafnium afyl; diisopropylanudoborane-bis-η5- (2-methylinden-1 -yl) hafnium η4-1,4-diphenyl-1,3-butadiene; diisopropylamidoborane-bis-T |5- (2-methylinden-1 -yl) hafnium T}4-2,4-hexadiene; diisopropylamidoborane-bis © - (2-methylinden-1 -yl) hafnium η4-1,4-dinaphthyl-1,3-butadiene; diisopropylamidoborane-bis-r |5- (2-methylmden-1 -yl) hafnium η4- 1-phenyl-1,3-pentadiene; diisopropylamidoborane-bis © - (2-methylinden-1 -yl) hafnium η4-1,3-pentadiene; diisopropylamidoborane-bis-u dichloride5- (2-methyl-4-phenylinden-l-yl) hafnium; diisopropylamidoborane-bis-Ti5- (2-methyl-4-phenylinden-l-yl) hafhio dimethyl; diisopropylamidoborane-bis ^ bis-dimethylamide5- (2-methyl-4-femlinden-l-yl) hafnium; diisopropylamidoborane-bis-r |5- (2-methyl-4-phenylinden-l-yl) hafmo 2-methyl-l, 3-butadiene; diisopropylamidoborane-bis-ii5- (2-methyl-4-phenylinden-l-yl) hafhio 2,3-dimethyl-1,3-butadiene; diisopropylamidoborane-bis-T)5- (2-methyl-4-phenylinden-l-yl) hafnium 2-N, N-dimethylaminobenzyl; diisopropylamidoborane-bis-rf- (2-methyl-4-phenylinden-l-yl) hafmo allyl; diisopropylamidoborane-bis-Ty- (2-methyl-4-phenylinden-l-yl) hafnium T)4-l, 4-diphenyl-1,3-butadiene;

diisopropylamidoborane-bis © - (2-methyl-4-phenylinden-l-yl) hafnium u4-2,4-hexadiene; diisopropylamidoborane-bis-r |5- (2-methyl-4-phenylinden-1 -yl) hafnium η4-1,4-dinaphthyl-1,3-butadiene;

diisopropylamidoborane-bis-T |5- (2-methyl-4-phenylinden-l-yl) hafTiio η4-1-phenyl-1,3-pentadiene; diisopropylamidoborane-bis ^5- (2-methyl-4-phenylinden-l-yl) hafnium η4-1,3-pentadiene; diisopropylamidoborane-bis-u dichloride5- (2-methyl-4-naphthylinden-l-yl) bafnium; diisopropylamidoborane-bis © - (2-methyl-4-naphthylinden-l-yl) hafhio dimethyl; bis-T diisopropylamidoborane-bis-dimethylamide |5- (2-methyl-4-naphthylinden-l-yl) hafmo; diisopropylamidoborane-bis-r |5- (2-methyl-4-naphthylinden-l-Il) there is 2-methyl-1,3-butadiene; diisopropylamidoborane-bis-r |5- (2-methyl-4-naphthylinden-l-yl) hafhio 2,3-dimethyl-1,3-butadiene; diisopropylamidoborane-bis-T |5- (2-methyl-4-naphthylinden-l-yl) hafhio 2-N, N-dimethylaminoben27

ES 2 188 235 T3 diisopropylamidoborane-bis © - (2-methyl-4-naphthylinden-l-yl) hafnium allyl; diisopropylamidoborane-bis-r |5- (2-Inethyl-4-naphthylinden-l-yl) hafhio T}4-l, 4-diphenyl-1,3-butadiene;

diisopropylamidoborane-bis-T |5- (2- [nethyl-4-naphthylinden-1 -yl) hafnium ti4-2,4-hexadiene; diisopropylamidoborane-bis-T |5- (2-methyl-4-naphthylinden-l-yl) hafnium T |4-l, 4-dinaphthyl-l, 3-buta · diene;

diisopropylamidoborane-bis-r |5- (2-methyl-4-naphthylinden-l-yl) hafnium ri4-l-phenyl-1,3-pentadiene; diisopropylainidoborane-bis-r |5- (2-methyl-4-naphthylinden-1 -yl) hafnium η4-1,3-pentadiene; diisopropylamidoborane-bis-r dichloride |5- (3-isopropylinden-l-yl) hafnium, diisopropylamidoborane-bis-η5- (3-isopropylinden-l-yl) hafhio dimethyl;

diisopropylamidoborane-bis © - (3-isopropylinden-l-yl) hafnium bis-dimethylamide; diisopropylamidoborane-bis © - (3-isopropylinden-l-yl) hafhio 2-methyl-1,3-butadiene; diisopropylamidoborane-bis-η5- (3-Isopropylinden-1-yl) hafnium 2,3-dimethyl-1,3-butadiene; diisopropylamidoborane-bis ^5- (3-isopropylinden-l-yl) hafhio 2-N, N-dimethylaminobenzyl; diisopropylamidoborane-bis ^5- (3-isopropylinden-l-yl) hafhio allyl;

diisopropylamidoborane-bis-p5- (3-isopropylinden-l-iI) hafhio η4-1,4-ΰϊ & ηί1-1,3-butadiene; diisopropylamidoborane-bis © - (3-isopropylinden-l-yl) hafhio η4-2,4-Ηεχ3 (1ίεηο; diisopropylamidoborane-bis © - (3-isopropylinden-l-yl) hafhio η4-1,4- <1ίη3ήί1-1,3-butadiene; diisopropylamidoborane-bis © - (3-isopropylinden-l-yl) hafhio η4-1-ίεηΐ1-1,3-ρεηίη <1ϊβηο; diisopropylamidoborane-bis © - (3-isopropylinden-1 -yl) hafnium η4-1,3-pentadiene; diisopropylamidoborane-bis dichloride ^5- {3-t-butylinden-l-yl) halhio; diisopropylamidoborane-bis © - (3-t-butylinden-l-yl) hafhio dimethyl; Diisopropylamidoborane-bis-p bis-dimethylamide5- (3-t-butylinden-l-yl) hafhio; diisopropylanudoborane-bis © - (3-t-butylinden-1-yl) hafnium 2-methyl-1,3-butadiene; diisopropylamidoborane-bis-η5- (3-t-butylinden-l-yl) hafhio 2,3-dimethyl-1,3-butadiene; diisopropylamidoborane-bis © - (3-t-butylinden-l-yl) hafhio 2-N, N-dimethylaminobenzyl; diisopropylamidoborane-bis-η5- (3-t-butylinden-l-yl) hafnium allyl;

diisopropylamidoborane-bis-η 5- (3-t-butylinden-1 -yl) hafnium η4-1,4-diphenyl-1,3-butadiene; diisopropylamidoborane-bis © - (3-t-butylinden-l-yl) hafhio q4-2,4-hexadiene; diisopropUamidoborane-bis ^5- (3-t-butylinden-l-yl) hafhk ^4-l, 4-dinaphthyl-l, 3-butadiene; diisopropylamidoborane-bis ^5- (3-t-butylinden-l-yl) liafhK ^4-l-phenyl-1,3-pentadiene; diisopropylamidoborane-bis © - (3-t-butylinden-l-yl) hafnium η4-1,3-ρβη1η <ϋβηο; bis (trimethylsilyl) amidoborane-bis-n dichloride5-cyclopentadienylhaphio; bis (trimethylsilyl) amidoborane-bis-η5-cyclopentadienylhainium dimethyl; bis (trimethylsilyl) amidoborane-bis ^ bis-dimethylamide5-cyclopentadienylhaphio; bis (trimethylsilyl) amidoborane-bis ^5-cyclopentadienylhafnium 2-methyl-1,3-butadiene; bis (trimethylsilyl) amidoborane-bis © -cyclopentadienylhafnium 2,3-dimethyl-1,3-butadiene; bis (trimethylsilyl) amidoborane-b¡s © -cyclopentadienylhaphio 2-N, N-dimethylaminobenzyl; bis (trimethylsilyl) amidoborane-bis © -cyclopentadienylhañuo allyl; bis (trimethylsilyl) amidoborane-bis © -cyclopentadienylhafhio η4-1,4- <1ϊ & ιιϊ1-1,3-butadiene; bis (trimethylsilyl) amidoborane-bis © -cyclopentadienylhafnium η4-2,4-1ιεχ3 (1ίβηο; bis (trimethylsilyl) amidoborane-bis © -cyclopentadienylhaíhio η4-1,4-άϊιΐ3βΐ1-1,3-butadiene;

ES 2 188 235 T3 bis (trimethylsilyl) amidoborane-bis-n5-cyclopentadienilhafiiion4-l-phenyl-1,3-pentadiene; bis (trimethylsilyl) amidoborane-bis-T |5- <; iclopentadienilhafhio r |5-l, 3-pentadiene; bis (trimethylsilyl) amidoborane-bis dichloride ^5-inden-l-ilhafnium; bis (trimethylsilyl) amidoborane-bis-rf-inden-l-ylhafhio dimethyl;

bis (trimethylsilyl) amidoborane-bis-r bis-dimethylamide |5-inden-l-ilhaftiio; bis (trimethylsilyl) amidoborane-bis-Ti5-inden-1 -ilhafnium 2-methyl-1,3-butadiene; bis (trimethylsilyl) amidoborane-bis-r |5-inden-l-ylhafnium 2,3-dimethyl-1,3-butadiene; bis (trimethylsilyl) amidoborane-bis-r |5-inden-l-ylhafhio 2-N, N-dimethylaminobenzyl; bis (trimethylsilyl) amidoborane-bis-q5-inden-l-ilhaíhio allyl;

bis (trimethylsilyl) amidoborane-bis-r |5-inden-l-ilhafnio T |4-l, 4-diphenyl-1,3-butadiene; bis (trimethylsilyl) amidoborane-bis-Ti5-inden-l-illiafmoTi4-2,4-hexadiene; bis (trimethylsilyl) amidoborane-bis-Ti5-inden-l-ilhafmoTi4-l, 4-dinaphthyl-l, 3-butadiene; bis (trimethylsilyl) amidoborane-bis-T |5-inden- l-ilhafnium η4- 1-phenyl-1,3-pentadiene; bis (trimethylsilyl) amidoborane-bis-T |5-inden-l-ilhafnium η4-1,3-pentadiene; bis (trimethylsilyl) amidoborane-bis-n dichloride5- (2-methylinden-l-yl) hafhio; bis (trimethylsilyl) amidoborane-bis-T |5- (2-methylinden-l-yl) hafinium dimethyl; bis (trimethylsilyl) amidoborane-bis-ri bis-dimethylamide5- (2-methylinden-l-yl) hafmo, bis (trimethylsilyl) amidoborane-bis-T |5- (2-methylinden-l-yl) hafnium 2-methyl-1,3-butadiene; bis (trimethylsilyl) amidoborane-bis-Ti5- (2-methylinden-l-yl) hafhio 2,3-dimethyl-1,3-butadiene; bis (trimethylsilyl) amidoborane-bis-r |5- (2-Inethylinden-l-yl) hafhio 2-N, N-dimethylaminobenzyl; bis (trimethylsilyl) amidoborane-bis-r |5- (2-methylinden-l-yl) hafhio allyl; bis (trimethylsilyl) amidoborane-bis-T)5- (2-methylinden-1 -yl) hafnium η4-1,4-diphenyl-1,3-butadiene; bis (trimethylsilyl) amidoborane-bis-T |5- (2-methylinden-1 -yl) hafnium r |4-2,4-hexadiene; bis (trimethylsilyl) amidoborane-bis-'n5- (2-methylinden-1 -yl) hafnium η4-1,4-dinaphthyl-1,3-butadiene; bis (thymmethylsilyl) amidoborane-bis-T)5- (2-methylinden-l-yl) hafnium r |4-l-phenyl-1,3-pentadiene; bis (trimethylsilii) amidoborane-bis-n5- (2-methylinden-l-yl) hafnium η4-1,3-pentadiene; bis (trimethylsilyl) amidoborane-bis-T dichloride |5- (2-methyl-4-phenylinden-l-yl) hafnium; bis (trimethylsilyl) amidoborane-bis-q5- (2-methyl-4-phenylinden-l-yl) hafiiio dimethyl; bis (trimethylsilyl) amidoborane-bis ^ bis-dimethylamide5- (2-methyl-4-phenylinden-l-yl) hafhio; bis (trimethylsilyl) amidoborane-bis-r |5- <2-methyl-4-feiulinden-l-yl) hafnium 2-methyl-l, 3-butadiene; bis (trimethylsilyl) amidoborane-bis-r |5- (2-methyl-4-phenylinden-l-yl) henium 2,3-dimethyl-1,3-butadiene;

bis (trimethylsilyl) amidoborane-bis-T |5- (2-methyl-4-pheiiilinden-l-yl) hafnium 2-N, N-dimethylaminobenzyl;

bis (trimethylsilyl) amidoborane-bis-T | 5- (2-methyl-4-phenylinden-1-yl) hafnium allyl; bis (trimethylsilyl) amidoborane-bis-T}5- (2-methyl-4-phenylinden-l-yl) hafnior |4-l, 4-diphenyl-1,3-butadiene;

bis (trimethylsilyl) amidoborane-bis-r |5- (2-methyl-4-phenylinden-l-yl) hafruo r |4-2,4-hexadiene; bis (trimethylsilyl) amidoborane-bis-r |5- (2-methyl-4-phenylinden-l -yl) hafnium η4-1,4-dinaphthyl-1,3-butadiene;

bis (trimethylsilyl) amidoborane-bis-r |S- (2-methyl-4-phenylmden-l-yl) hafmo r / -l-phenyl-1,3-pentadiene;

ES 2 188 235 T3 bis (trimethylsilyl) amidoborane-bis-n5- (2-methyl-4-phenylinden-1 -yl) hafnium η4-1,3-pentadiene; bis (trimethylsilyl) amidoborane-bis-i- dichloride |5- (2-methyl-4-naphthylindcn-l-yl) hafnium; bis (trimethylsilyl) amidoborane-bis-rf- (2-methyl-4-naphthylmden-1-yl) hafmo dimethyl; bis (trimethylsilyl) amidoborane-bis ^ bis-dimethylamide5- (2-methyl-4-naphthylinden-l-yl) hafhio; bis (trimethylsilyl) amidoborane-bis-r |5- (2-methyl-4-naphthylinden-l-yl) hafnium 2-methyl-l, 3-butadiene, bis (trimethylsilyl) amidoborane-bis-r / - (2-methyl-4-naphthylinden-l-yl) hafnium 2,3-dimethyl-1,3-butadiene;

bis (trinyethylsilyl) amidoborane-bis-Ti5- (2-methyl-4-naphthylinden-l-yl) hafhio 2-N, N-dimethylaminobenzyl;

bis (trimethylsilyl) ainidoborane-bis-Ti5- (2-methyl-4-naphthylinden-l -yljhafnium allyl; bis (trimethylsilyl) amidoborane-bis-r |5- (2-Inethyl-4-naphthylinden-l-yl) hafiiio Ti4-l, 4-diphenyl-1,3-butadiene;

bis (trimethylsilyl) amidoborane-bis-Ti5- (2-niethyl-4-naphthylinden-l-yl) hainium T}4-2,4-hexadiene; bis (trimethylsilyl) amidoborane-bis-T |5- (2-methyl-4-iiaphthylinden-l-yl) hafnium ti4-l, 4-dinaphthyl-l, 3-butadiene;

bis (trimethylsilyl) amidoborane-bis-Ti5- (2-methyl-4-iiaphthylinden-l-yl) hafnium T |4-l-phenyl-1,3-pentadiene;

bis (trimethylsilyl) amidoborane-bis-T |S- (2-methyl-4-naphthylinden-l-yl) hafhio r |4-l, 3-pentadiene; bis (trimethylsilyl) amidoborane-bis-T dichloride |5- (3-isopropylinden-l-yl) hafnium; bis (trimethylsilyl) amidoborane-bis-T |5- (3-isopropylinden-l-yl) hafmo dimethyl; bis (trimethylsilyl) amidoborane-bis ^ bis-dimethylamide5- (3-isopropylinden-l-yl) hafnium; bis (trimethylsiliI) amidoborane-b¡sr |5- (3-Isopropylinden-1 -yljhafnium 2-methyl-1,3-butadiene; bis (trimethylsilyl) aimdoborane-bis-T |S- (3-isopropylinden-l-yl) hafnium 2,3-dimethyl-1,3-butadiene; bis (trimethylsilyl) amidoborane-bis-T}5- (3-isopropylinden-l-yl) hafnium 2-N, N-dimethylaminobenzyl;

bis (trimethylsilyl) amidoborane-bis-T |5- (3-isopropylinden-l-yl) hafhio allyl; bis (trimethylsilyl) amidoborane-bis-r |5- (3-isopropylinden-l-yl) hafnium η4- 1,4-diphenyl-1,3-butadiene;

bis (trimethylsilyl) amidoborane-bis-Ti5- (3-isopropylinden-l-yl) hafnium r |4-2,4-hexadiene; bis (trimethylsilyl) amidoborane-bis-Ti5- (3-isopropylinden-l-yl) hafnium r |4-l, 4-dinaphthyl-l, 3-butadiene;

bis (trimethylsilyl) amidoborane-bis-n5- (3-isopropylinden-l-yl) hafnium p4-l-phenyl-1,3-pentadiene; bis (trimethylsilyl) amidoborane-bis-ris- (3 -isopropylinden-1 -yljhafnium η4-1,3-pentadiene; bis (trimethylsilyl) amidoborane-bis dichloride ^5- (3-t-butylinden-l-yljhafnium; bis (trimethylsilyl) amidoborane-bis-Ti5- (3-t-butylinden-l-yl) hafnium dimethyl; bis (trimethylsilyl) amidoborane-bis-n bis-dimethylamide5- (3-t-butylinden-l-yl) hafnium; bis (trimethylsilyl) amidoborane-bis-Ti5- (3-t-butylinden-1-yl) hafnium 2-methyl-1,3-butadiene; bis (triinethylsilyl) amidoborane-bis-Ti5- (3-t-butylinden-l-yl) hafnium 2,3-dimethyl-1,3-butadiene; bis (trimethylsilyl) amidoborane-bis-r |5- (3-t-butylinden-l-yl) 2-N, N-dimethylaminobenzyl; bis (trimethylsilyl) amidoborane-bis-T)5- (3-t-butylinden-l-yl) hafhio allyl;

bis (trimethylsilyl) amidoborane-bis-Ti5- (3-t-butylinden-l-yl) hafhioii4-l, 4-diphenyl-1,3-butacliene; bis (trimethylsilyl) amidoborane-bis-T |5- (3-t-butylinden-l-yl) hafhio -q4-2,4-hcxadiene;

ES 2 188 235 T3 bis (trimethylsiUl) amidoborane-bis-T |5- (3-t-butylinden-l-yl) hafniumTi4-l, 4-dinaphthyl-l, 3-butadiene; bis (trimethylsilyl) amidoborane-bis-r |5- (3-t-butylinden-1 -yl) hafnium η4-1-phenyl-1,3-pentadiene; bis (trimethylsilyl) amidoborane-bis-Ti5- (3-t-butylinden-l-yl) hafnium η4-1,3-pentadiene; bis (diisopropylamido) diborane-1,2-bis - ^ - (2-methyl-4-phenylinden-1-yl) hafnium dichloride; bis (diisopropylamido) diborane-1,2-bis-T |5- (2-methyl-4-phenylinden-1 -yl) hafnium dimethyl; bis (diisopropylamido) diborane-1,2-bis-T bis-dimethylamide |5- (2-methyl-4-phenylinden-1-yl) hafnium;

bis (diisopropylamido) diborane-1,2-bis-r |5- (2-methyl-4-phenylinden-l-yl) hafnium 2-methyl-1,3-butadiene;

bis (diisopropylamido) diborane-1,2-bis-r |5- (2-methyl-4-phenylinden-l-yl) hafhio 2,3-dimethyl-1,3-butadiene;

bis (diisopropylamido) diborane-1,2-bis-r |5- (2-methyl-4-phenylinden-1-yl) hafnium 2-N, N-dimethylaminobenzyl;

bis (diisopropylainido) diborane-1,2-bis-T |S- (2-Inethyl-4-phenylinden-l-yl) hafhio allyl; bis (diisopropylaniido) diborane-1,2-bis-Ti5- (2-methyl-4-phenylinden-l-yl) hafnium T |4-l, 4-diphenyl-1,3-butadiene;

bis (diisopropylamido) diborane-1,2-bis-r |5- (2-methyl-4-phenylinden-l-yl) hafnium r |4-2,4-hexadiene; bis (diisopropylamido) diborane-1,2-bis ^5- (2-methyl-4-phenylinden-l-yl) hafhio T}4-l, 4-dinaphthyl1,3-butadiene;

bis (diisopropylamido) diborane-1,2-bis-Tj5- (2-methyl-4-phenylinden-l-yl) hafnium η4-1-phenyl-1,3pentadiene;

bis (diisopropylamido) diborane-1,2-bis - ^ - (2-methyl-4-phenylinden-1-yl) zirconium η4-1,3-pentadiene;

(^ -tetramethylcyclopentadienylXtert-butylamido) diisopropylamidoborane titanium dichloride; (T |5-tetramethylcyclopentadienyl) (tert-butylamido) diisopropylamidoborane titanium dimethyl; (© tetramethylcyclopentadienyl) (tere-butylamido) diisopropylamidoborane titanium bis-trimethylamide;

(r |5-tetramethylcyclopentadieml) (tert-butylamido) diisopropylamidoborane titanium 2-methyl-1,3-butadiene;

(Tl5-tetramethylcyclopentadienyl) «c-butylamido) diisopropylamidoborane titanium 2,3-dimethyl-1,3-butadiene;

(r |5-tetramethylcyclopentadienyl) «c-butylamido) diisopropylamidoborane titanium 2-N, N-dimethylaminobenzyl;

(r |5-tetramethylcyclopentadienyl) «e-butylamido) diisopropylamidoborane titanium allyl; (You5-tetramethylcyclopentadienyl) (ert-butiiamido) diisopropylamidoborane titanium 1,4-diphenyl1,3-butadiene;

(T |5-tetramethylcyclopentadienyl) (ert-butylamido) diisopropylamidoborane titanium r |4-2,4-hexadiene;

(You5-tetramethylcyclopentadienyl) (ert-butylamido) diisopropylamidoborane titanium t}4-l, 4-dinaphthyl-l, 3-butadiene;

(Tl5-tetramethylcyclopentadienyl) (/ erc-butylamido) diisopropylamidoborane titanium η4-1- & ηϊ1-1,3pentadiene;

ES 2 188 235 T3 teMetramethylcyclopentadienyl) (tert-butylamido) dnsopn} pilamidoborane titanium T |4-l, 3-pentadiene;

dichloride ('q5-tetramethylcyclopentadienyl) (cyclohexylamido) diisopropylamidoborane titanium; Ol5-tetramethylcyclopentadienyl) (cyclohexylamido) diisopropylamidoborane titanium dimethyl; bis-dimethylamide of (r¡5-tetramethylcyclopentadienyl) (cycloyexylamido) diisopropylainidoborane titanium;

(r |5-tetramethylcyclopentadienyl) (cyclohexylamido) diisopropylamidoborane titanium 2-methyl-1,3-butadiene;

(r)5-tetramethylcyclopentadienyl) (cyclohexylamido) dnsopropylainideborane titanium 2,3-dimethyl1.3-butadiene;

(T |5-tetramethylcyclopentadienyl) (cyclohexylamido) diisopropylamidoborane titanium 2-N, N-dimethylaminobenzyl;

(r |5-tetramethylcyclopentadienyl) (cyclohexylamido) diisopropylamidoborane titanium allyl; tea5-tetramethylcyclopentadienyl) (cyclohexylamido) diisopropylamidoborane titanium ri4-l, 4-diphenyl-1,3-butadiene;

(• r |5-tetramethylcyclopentadienyl) (cyclohexylamido) diisopropylamidoborane titanium r)4-2,4-hexadiene;

(r |5-tetrainethylcyclopentadienyl) (cyclohexylamido) diisopropylainidoborane titanium -q4-l, 4-dinaphthyl-l, 3-butadiene;

(• q5-tetramethylcyclopentadienyl) (cyclohexylanudo) dnsopropylamidoborane titanium η4-1- & ηϊ11.3- pentadiene;

(You5-tetramethylcyclopentadienyl) (cyclohexylamido) diisopropylamidoborane titanium η4-1,3-pentadiene;

dichloride of (r |5-tetramethylcyclopentadienyl) (tert-butylamido) bis (diisopropylamide) diborane titanium;

(^ -tetramethylcyclopentadienyl) (tert-butylamido) bis (diisopropylamide) diborane titanium dimethyl;

bis-dimethylamide of (r |5-tetramethylcyclopentadienyl) (eerc-butylamido) bis (diisopropylamide) diborane titanium;

(r |5-tetramethylcyclopentadienyl) (eere-butylamido) bis (diisopropylamide) diborane titanium 2-methyl1.3-butadiene;

(r |5-tetramethylcyclopentadienyl) (/ erc-butylamido) bis (diisopropylamide) diborane titanium 2,3-dimethyl-1,3-butadiene;

(r |5-tetramethylcyclopentadienyl) (/ e / -c-butylamdo) bis (diisopropylamide) diborane titanium 2-N, N-dimethylaminobenzyl;

(n5-tetramethylcyclopentadienii) (eerc-butylamido) bis (diisopropylamide) diborane titanium allyl; (r |5-tetramethylcyclopentadienyl) (feTC-butylamdo) bis (diisopropylamide) diborane titanium η4-1,4-diphenyl-1,3-butadiene;

(T |5-tetramethylcyclopentadienyl) (tert-butylamido) bis (diisopropylamide) diborane titanium η4-2.4hexadiene;

(T |5-tetraniethylcyclopentadieml) (tert-butylamido) bis (diisopropylamide) diborane titanium η4-1,4dinaphthyl-1,3-butadiene;

ES 2 188 235 T3 (n5-tetramethylcyclopentadienyl) (tert-butylamido) bis (diisopropylamide) diborane titanium η4-1phenyl-1,3-pentadiene;

(what5-tetramethylcyclopentadienyl) (forc-butylamido) bis (diisopropylamide) diborane titanium η4-1,3pentadiene;

dichloride of (r |5-tetramethylcyclopentadienyl) (phenylamido) diisopropylamidoborane titanium; (r |5-tetramethylcyclopentadienyl) (phenylainido) diisopropylamidoborane titanium dimethyl; ^ bis-dimethylamide5-tetramethylcyclopentadienyl) (phenylamido) diisopropylamidoborane titanium;

(You5-tetramethylcyclopentadienyl) (phenylamido) diisopropylamidoborane titanium 2-methyl-1,3-butadiene;

(r |5-tetramethylcyclopentadienyl) (phenylamido) diisopropylainidoborane titanium 2,3-dimethyl-1,3-butadiene;

(r |5-tetramethylcyclopentadienyl) (phenylamido) diisopropylamidoborane titanium 2-N, N-dimethylaminobenzyl;

(T |5-tetramethylcyclopentadienyl) (phenylamido) diisopropylamidoborane titanium allyl; (r |5-tetramethylcyclopentadienyl) (femlamido) diisopropylamidoborane titanium rf-l, 4-diphenyl-l, 3-butadiene;

(r |5-tetramethylcyclopentadienyl) (phenylamido) diisopropylamidoborane titanium r |4-2,4-hexadiene; (r |5-tetramethylcyclopentadieml) (femlaimdo) diisopropylainidoborane titanium η4-1,4-dinafyl-1,3-butadiene;

(i- |5-tetramethylcyclopentadienyl) (phenylamido) diisopropylaniidoborane titanium η4-1-phenyl-1,3-pentadiene;

(p5-tetramethylcyclopentadienyl) (phenylamido) diisopropylamidoborane titanium T |4-l, 3-pentadiene; (^ -tetramethylcyclopentadienyl) (ert-butylamido) dimethylamidoborane titanium dichloride; (r |S-tetramethylcyclopentadienyl) (phere-butylamido) dimethylamidoborane titanium dimethyl; bis-dimethylamide of (n5-tetramethylcyclopentadienyl) (tert-butylamido) dimethylamidoborane titanium;

(what5-tetramethylcyclopentadieml) (ert-butylamido) dimethylamidoborane titanium 2-methyl-1,3-butadiene;

(what5-tetramethylcyclopentadienyl) (ert-butylamido) dimethylamidoborane titanium 2,3-dimethyl-1,3-butadiene;

(T |5-tetramethylcyclopentadienyl) (tert-butylamido) dimethylamidoborane titanium allyl; ^5-tetramethylcyclopentadienyl) (eerc-butylamido) dimethylamidoborane titanium rf-1,4-diphenyl-1,3-butadiene;

(© tetramethylcyclopentadienyl) (tert-butylamido) dimethylamidoborane titanium η4 2,4-hexadiene; (© tetramethylcyclopentadienyl) (tert-butylamido) dimethylamidoborane titanium Ti4-l, 4-dinafyl1,3-butadiene;

(what5-tetramethylcyclopentadienyl) (eerc-butylamido) dimethylamidoborane titanium n4-l, 3-pentadiene;

ES 2 188 235 T3 (p5-inden-l-yl) (Zerc-butylamido) diisopropylamidoborane titanium; (• q5-inden-l-yl) (/ erc-butylamido) diisopropylamidoborane titanium dimethyl; bis-dimethylamide of (r |5-inden-l-yl) (eerc-butylamido) diisopropylamidoborane titanium; (ri5-inden-l-yl) (/ ere-butylamido) diisopropylamidoborane titanium 2-methyl-1,3-butadiene; (r |5-inden-1-yl) (Zerc-butylamido) diisopropylamidoborane titanium 2,3-dimethyl-1,3-butadiene; (T |5-Inden-l-yl) (rere-butylamido) diisopropylamidoborane titanium 2-N, N-dimethylaminobenzyl; (T |5-inden-l-yl) (ert-butylamido) diisopropylamidoborane titanium allyl; (Tl5-inden-li]) (tert-butylamido) diisopropylamidoborane titanium q4-l, 4-diphenyl-1,3-butadiene; (T |5-inden-l-yl) (tert-butylamido) diisopropylamidoborane titanium Tj4-2,4-hexadiene;

(r |5-inden-1 -yl) (tert-butylamido) diisopropylamidoborane titanium η4-1,4-dinafyl-1,3-butadiene; (r |5-inden-l-yl) (phere-butylamido) diisopropylamidoborane titanium η4-1-phenyl-1,3-pentadiene; (r |5-inden-l-yl) (fcrc-butylamido) diisopropylamidoborane titanium T |4-l, 3-pentadiene; dichloride (T |5-2,3-dimethyl-1 -) (ferc-butylamido) diisopropylamidoborane titanium; ^5-2,3-dimethylinden-l-yl) (Zerc-butylamido) diisopropylamidoborane titanium dimethyl; (^ -2,3-dimethylinden-l-yl) (tert-butylainido) diisopropylamidoborane titanium bis-dimethylamide;

(n5-2,3-dimethylinden-l-yl) (forc-butylamido) diisopropylamidoborane titanium 2-methyl-1,3-butadiene;

(η5-2,3-dimethylinden-l-yl) (tert-butylamido) diisopropylamidoborane titanium 2,3-dimethyl-1,3-butadiene;

(η5-2,3-dimethylinden-1-yl) (tert-butylamido) diisopropylamidoborane titanium 2-N, N-dimethylaminobenzyl;

(r |5-2,3-dimethylinden-l-yl) (tert-butylamido) diisopropylamidoborane titanium allyl; (© 2,3-dimethylinden-l-yl) (tert-butylamido) diisopropylaniidoborane titanium r |4-l, 4-difeml-l, 3-butadiene;

(T]5-2,3-dimethylinden-l-yl) (tere-butylamido) düsopropylainidoborane titanium q4-2,4-hexadiene; (ijs-2,3-dimethylinden-l-yl) (tert-butylamido) diisopropylaimdoborane titanium iq4-l, 4-dmaphthyl-l, 3-butadiene;

(You5-2,3-dimethylinden-l-yl) (ferc-butylamido) diisopropylamidoboraiium titanium r |4-l-phenyl-1,3-pentadiene;

(n5-2,3-dimethylinden-l-yl) (/ erc-butylamido) diisopropylamidoborane titanium if-l, 3-pentadiene; (Tf-2-pyrrolidenylinden-l-yl) (tert-butylamido) diisopropylamidoborane titanium dichloride; (T}5-2-pinOIidenylinden-l-yl) (ert-butylamido) diisopropylaimdot> orano titanium dimethyl; 0i bis-dimethylamide5-2-pyrrolidenylinden-l-yl) (phere-butylamido) diisopropylamidoborane titanium;

(Tl5-2-pyrrolidenylinden-l-yl) (Zere-butylamido) diisopropylamidoborane titanium 2-methyl-1,3-butadiene;

^5-2-pyrrolidenylinden-l-yl) (tert-butylamido) diisopropylamidoborane titanium 2,3-dimethyl-1,3-butadiene;

(r |5-2-pyrrolidemlinden-l-yl) (ferc-butylamido) diisopropylamidoborane titanium 2-N, N-dimethylaminobenzyl;

(• r |5-2-pyrrolidemlinden-l-yl) (eere-butylamido) diisopropylainidoborane titanium allyl;

ES 2 188 235 T3 (r |5-2-pyrrolidenylinden-l-yl) (phere-butylamido) diisopropylamidoborane titanium η4-1,4- <ϋίβηϊ11,3-butadiene;

rá5-2-pyrrolidenylinden-l-yl) (tert-butylamido) diisopropylamidoborane titanium ^ -2,4-hexadiene;

(r |5-2-pyrrolidemlinden-l-yl) (ert-butylamido) diisopropylamidoborane titanium Ti4-l, 4-dinaphthyl1,3-butadiene;

^5-2-pyrrolidenylinden-l-yl) (ert-butylamido) diisopropylamidoborane titanium r |4-l-phenyl-1,3-pentadiene;

(You5-2-pyrrolidenylinden-l-yl) (tert-butylamido) diisopropylamidoborane titanium r |4-l, 3-pentadiene;

bis-phenylamido-bis (diisopropylamido) diborane titanium dichloride; bis-phenylamido-bis (diisopropylamido) diborane titanium dimethyl; bis-phenylamido-bis (diisopropylamido) diborane titanium bis-dimethylamide; bis-phenylamido-bis (diisopropylamido) diborane titanium 2-methyl-1,3-butadiene; bis-phenylamido-bis (diisopropylainide) diborane titanium 2,3-dimethyl-1,3-butadiene; bis-phenylamido-bis (diisopropylamido) diborane titanium 2-N, N-dimethylaminobenzyl; bis-phenylamido-bis (diisopropylamido) diborane titanium allyl; bis-phenylamido-bis (diisopropylainido) diborane titanium r |4-l, 4-diphenyl-1,3-butadiene; bis-phenylamido-bis (diisopropylamido) diborane titanium r |4-2,4-hexadiene; bis-phenylamido-bis (diisopropylamido) diborane titanium T)4-l, 4-dinaphthyl-l, 3-butadiene; bis-phenylamido-bis (diisopropylamido) diborane titanium T)4-l-phenyl-1,3-pentadiene; bis-phenylamido-bis (diisopropylamido) diborane titanium r |4-l, 3-pentadiene; bis-2,6-diisopropylphenylamido-bis (diisopropylamido) diborane titanium dichloride; bis-2,6-diisopropylphenylamido-bis (diisopropylainido) diborane titanium dimethyl; bis-2,6-diisopropylphenylamido-bis (diisopropylamido) diborane titanium bis-dimethylamide; bis-2,6-diisopropylphenylamido-bis (diisopropylamido) diborane titanium 2-methyl-1,3-butadiene; bis-2,6-diisopropylphenylamido-bis (diisopropylamido) diborane titanium 2,3-dimethyl-1,3-butadiene;

bis-2,6-diisopropylphenylamido-bis (diisopropylamido) diborane titanium 2-N, N-dimethylaminobenzyl;

bis-2,6-diisopropylphenylamido-bis (diisopropylamido) diborane titanium allyl; bis-2,6-diisopropylphenylamido-bis (diisopropylamido) diborane titanium η4-1,4-diphenyl-1,3-butadiene;

bis-2,6-diisopropylphenylamido-bis (diisopropylamido) diborane titanium r |4-2,4-hexadiene; bis-2,6-diisopropylphenylamido-bis (diisopropylamido) diborane titanium Ti4-l, 4-dinaphthyl-l, 3-butadiene;

bis-2)6-diisopropylphenylamido-bis (diisopropylamido) diborane titanium T |4-l-phenyl-1,3-pentadiene;

bis-2,6-diisopropylphenylamido-bis (diisopropylamido) diborane titanium r |4-l, 3-pentadiene; bis-3,5-dimethylbenzylamido-bis (dimethylamido) diborane titanium dichloride; bis-3,5-dimethylbenzylamido-bis (dimethylamido) diborane titanium dimethyl; bis-3,5-dimethylbenzylamido-bis (dimethylamido) diborane titanium bis-dimethylamide; bis-3,5-dimethylbenzylamido-bis (dimethylamido) diborane titanium 2-methyl-1,3-butadiene; bis-3,5-diinethylbenzylamido-bis (dinyethylamido) diborane titanium 2,3-dimethyl-1,3-butadiene;

ES 2 188 235 T3 bis-3,5-dimethylbenzylamido-bis (dimethylamido) diborane titanium 2-N, N-dimethylaminobenzyl; bis-3,5-dimethylbenzylamido-bis (dimethylamido) diborane titanium allyl; bis-3,5-dimethylbenzylamido-bis (dimethylamido) diborane titanium T |4-l, 4-diphenyl-1,3-butadiene; bis-3,5-dimethylbenzylamido-bis (dimethylamido) diborane titanium T |4-2,4-hexadiene; bis-3,5-dimethylbenzylamido-bis (dimethylamido) diborane titanium η4-1,4-dinaphthyl-1,3-butadiene; bis-3,5-dimethylbenzylamido-bis (dimethylamido) diborane titanium r |4-l-phenyl-1,3-pentadiene; bis-3,5-dimethylbenzylamido-bis (dimethylamido) diborane titanium T)4-l, 3-pentadiene; bis-2,6-dimethylbenzylamido-bis (dimethylainido) diborane titanium dichloride; bis-2,6-dimethylbenzylamido-bis (dimethylainido) diborane titanium dimethyl; bis-2,6-dimethylbenzylamido-bis (dinyethylamido) diborane titanium bis-dimethylamide; bis-2, o-dimethylbenzylamido-bis (dimethylainido) diborane titanium 2-methyl-1,3-butadiene; bis-2,6-dimethylbenzylamido-bis (dimethylamido) diborane titanium 2,3-dimethyl-1,3-butadiene; bis-2,6-dimethylbenzylamido-bis (dimethylamido) diborane titanium 2-N, N-dimethylaminobenzyl; bis-2,6-dimethylbenzylamido-bis (dimethylamido) diborane titanium allyl; bis-2,6-dimethylbenzylamido-bis (dimethylamido) diborane titanium ii4-l, 4-diphenyl-1,3-butadiene; bis-2,6-dimethylbenzylamido-bis (dimethylamido) diborane titanium r |4-2,4-hexadiene; bis-2,6-dimethylbenzylamido-bis (dimethylamido) diborane titanium η4-1,4-dinaphthyl-1,3-butadiene; bis-2,6-dimethylbenzylamido-bis (dimethylamido) diborane titanium T]4-l- phenyl-1,3-pentadiene; bis-2,6-dimethylbenzylamido-bis (dimethylamido) diborane titanium η4-1,3-pentadiene; bis-2,6-diisopropylphenylamido-bis (dimethylamido) diborane titanium dichloride; bis-2,6-diisopropylphenylamido-bis (dimethylamido) diborane titanium dimethyl; bis-2,6-diisopropylphenylamido-bis (dimethylamido) diborane titanium bis-dimethylamide; bis-2,6-diisopropylphenylamido-bis (dimethylamido) diborane titanium 2-methyl-1,3-butadiene; bis-2,6-diisopropylphenylamido-bis (dimethylamido) diborane titanium 2,3-dimethyl-1,3-butadiene; bis-2,6-diisopropylphenylamido-bis (dimethylamido) diborane titanium 2-N, N-dimethylaminobenzyl; bis-2,6-diisopropylphenylamido-bis (dimethylamido) diborane titanium allyl; bis-2,6-diisopropylphenylamido-bis (dimethylamido) diborane titanium Tf-l, 4-diphenyl-l, 3-butadiene; bis-2,6-diisopropylphenylamido-bis (dimethylamido) diborane titanium Ti4-2,4-hexadiene; bis-2,6-diisopropylphenylamido-bis (dimethylamido) diborane titanium Ti4-l, 4-dinafyl-l, 3-butadiene;

bis-2,6-diisopropylphenylamido-bis (dimethylamido) diborane titanium T |4-l-phenyl-1,3-pentadiene; bis-2,6-diisopropylphenylamido-bis (dimethylamido) diborane titanium r |4-l, 3-pentadiene; bis-2,6-diisopropylphenylamido-bis (bis (trimethylsilyl) amido) diborane titanium dichloride; bis-2,6-diisopropyl] phenylamido-bis (bis (trimethylsilyl) ainido) diborane titanium dimethyl; bis-2,6-diisopropylphenylamido-bis (bis (trimethylsilyl) amido) diborane titanium bis-dimethylamide; bis-2,6-diisopropylphenylantido-bis (bis (trimethylsilyl) amido) diborane titanium 2-methyl-1,3-butadiene;

bis-2,6-diisopropylphenylamido-bis (bis (trimethylsilyl) amido) diborane titanium 2,3-dimethyl-1,3-butadiene;

bis-2,6-diisopropylphenylamido-bis (bis (trimethylsilyl) amido) diborane titanium 2-N, N-dimethylaminobenzyl;

bis-2,6-diisopropylphenylamido-bis (bis (trimethylsilyl) amido) diborane titanium allyl; bis-2,6-diisopropylphemlamido-bis (bis (trimethylsilyl) amido) diborane titanium η4-1,4-ύϊίβηί1-1,3butadiene;

ES 2 188 235 T3 bis-2,6-diisopropylphenylamido-bis (bis (trimethylsilyl) amido) diborane titanium rf-2,4-hexadiene; bis-2,6-diisopropylphenylamido-bis (bis (trimethylsilyl) ainido) diborane titanium ti4-l, 4-dinaphthyl-1,3-butadiene;

bis-2,6-diisopropylphenylamido-bis (bis (trimethylsilyl) amido) diborane titanium η4-1-phenyl-1,3-pentadiene;

bis-2,6-diisopropylphenylamido-bis (bis (trimethylsilyl) amido) diborane titanium η4-1,3-pentadiene; bis-2,6-diisopropylphenylamido-bis (diisopropylamido) diborane zirconium dichloride; bis-2,6-diisopropylphenylamido-bis (diisopropylamido) diborane zirconium dimethyl; bis-2,6-diisopropylphenylamido-bis (diisopropylamido) diborane zirconium bis-dimethylamide; bis-2,6-diisopropylphenylamido-bis (diisopropylamido) diborane zirconium 2-methyl-1,3-butadiene; bis-2,6-diisopropylphenylamido-bis (diisopropylamido) diborane zirconium 2,3-dimethyl-1,3-butadiene;

bis-2,6-diisopropylphenylamido-bis (diisopropylamido) diborane zirconium 2-N, N-dimethylaminobenzyl;

bis-2,6-diisopropylphenylamido-bis (diisopropylamido) diborane zirconium allyl; bis-2,6-diisopropylphenylamido-bis (diisopropylamido) diborane zirconium ^ -l, 4-diphenyl-l, 3-butadiene;

bis-2,6-diisopropylphenylamido-bis (diisopropylamido) diborane zirconium T]4-2,4-hexadiene; bis-2,6-diisopropylphenylamido-bis (diisopropylamido) diborane zirconium T |4-l, 4-dinaphthyl-l, 3-butadiene;

bis-2,6-diisopropylphenylamido-bis (diisopropylamido) diborane zirconium r |4-l-phenyl-1,3-pentadiene;

bis-2,6-diisopropylphenylamido-bis (diisopropylamido) diborane zirconium i]4-l, 3-pentadiene; bis-2-tert-butylphenylamido-bis (diisopropylamido) diborane titanium dichloride; bis-2-Zerc-butylphenylamido-bis (diisopropylamido) diborane titanium dimethyl; bis-2- / erc-butylphenylamido-bis (diisopropylamido) diborane titanium bis-dimethylamide; bis-2- / erc-butylphenylamido-bis (diisopropylamido) diborane titanium 2-methyl-1,3-butadiene; bis-2-ert-butylphenylamido-bis (diisopropylamido) diborane titanium 2,3-dimethyl-1,3-butadiene; bis-2-Zerc-butylphenylamido-bis (diisopropylamido) diborane titanium 2-N, N-dimethylaminobenzyl; bis-2- / erc-butylphenylamido-bis (diisopropylamido) diborane titanium allyl; bis-2-tert-butylphenylamido-bis (diisopropylamido) diborane titanium η4-1,4- <Ιϊ & ηΐ1-1,34ηιΐ3diene;

bis-2-tert-butylphenylamido-bis (diisopropylamido) diborane titanium r |4-2,4-hexadiene; bis-2-eerc-butylphenylamido-bis (diisopropylamido) diborane titanium T |4-l, 4-dinaphthyl-l, 3-butadiene;

bis-2-eerc-butylphenylamido-bis (diisopropylamido) diborane titanium i]4-l-phenyl-1,3-pentadiene; and bis-2-tert-butylphenylamido-bis (diisopropylamido) diborane titanium η4-1,3-pentadiene.

Another preferred class of Group 4 transition metal complexes of the present invention are represented in formulas 4-9 defined previously, where T is:

IS 2 188 235 T3

including structures in which two R groups are attached1 and R5, such as in 1,3,4,6,7,8, hexahydro-pyrimido [1,2-a] pyrimidinate, shown below:

In the above species, it is believed, without intention to be bound by such belief, that the ligand group, T, is connected to Z through its heteroatoms.

Specific, but not limiting, examples of the above metal complexes included within the invention are:

N, N * -diisopropyl-phenyl-amidylate borane-bis-q dichloride5-cyclopentadienylzirconium; N, N'-diisopropyl-phenyl-amidinate borane-bis-q5-cyclopentadienylzirconium dimethyl; Ν, Ν'-diisopropyl-phenyl-borane-bis-q bis-dimethylamide5-cyclopentadienylzirconium; Ν, Ν'-diisopropyl-phenyl-amidinate borane-bis - ^ - cyclopentadienylzirconium 2-methyl-1,3-butadiene;

Ν, Ν'-düsopropyl-phenyl-amidinate borane-b¡sr |5-cyclopentadiemlzirconium 2,3-dimethyl-1,3-butadiene;

Ν, Ν'-diisopropyl-phenyl-amidinate borane-bis-rf-cyclopentadienylzirconium 2-N, N-dimethylami · nobenzyl;

Ν, Ν'-diisopropyl-phenyl-amidinate borane-bis ^5-cyclopentadienylzirconium allyl; Ν, Ν'-diisopropyl-feml-borane-bis-q amidinates-cyclopentadienylzirconium q4-l, 4-diphenyl-l, 3 · butadiene;

N.N'-diisopropyl-phenyl-amidinate borane-bis-η 5-cyclopentadienylzirconium q4-2,4-hexadiene; Ν, Ν'-düsopropyl-phenyl-amidinate borane-bis-r |5-cyclopentadienylzirconium q4-l, 4-dinaphthyl-l, 3-butadiene;

Ν, Ν'-diisopropyl-phenyl-amidinate borane-bis-q5-cyclopentadienylzirconium η4- l-phenyl-l, 3-pentadiene;

N.N'-diisopropyl-phenyl-amidinate bor <mo-bis-q5-cyclopentadienylzirconium q4-l, 3-pentadiene; N, N dichloridel-diisopropyl-3-phenyl-l, 3-diketimine borane-bis-η 5-cyclopentadienylzirconium; N, N'-diisopropyl-3-phenyl-1,3-diketimine borane-bis-q5-cyclopentadienylzirconium dimethyl; N, N bis-dimethylamidel-diisopropyl-3-phenyl-l, 3-diketimine borane-bis-q5-cyclopentadienyl zirconium;

N, N'-diisopropyl-3-phenyl-1,3-dichotimine borane-bis-η s-cyclopentadienylzirconium 2-methyl-1,3 butadiene;

N, N'-diisopropyl-3-phenyl-1,3-diketimine borane-bis-T |5-cyclopentadienylzirconium 2,3-dimethyl1,3-butadiene;

IS 2 188 235 T3

Ν, Ν1 -diisopropyl-3-phenyl-1,3-diketimine borane-bis-T ^ -cyclopentadienylzirconium 2-N, N-dimethylaminobenzyl;

N, N'-diisopropyl-3-phenyl-1,3-diketimine borane-bis-T ^ -cycIopentadienylzirconium allyl; N, N,-diisopropyl-3-phenyl-l, 3-diketimineborane-bis ^5-cyclopentadienylzirconium ri4-l, 4-diphenyl-1,3-butadiene;

N, N'-diisopropyl-3-phenyl-1,3-diketimine borane-bis-r |5-cyclopentadienylzirconium Y4-2,4-hexadiene;

N, N'-diisopropyl-3-phenyl-1,3-diketimine borane-bis-u5-cyclopentadiemlzirconium ti4-l, 4-dinaphthyl-1,3-butadiene;

N, N'-diisopropyl-3-feml-1,3-diketimineborane-bis-Tf-cyclopentadienylzirconiumT |4-l-phenyl-1,3-pentadiene;

N, N'-diisopropyl-3-phenyl-1,3-diketiinin borane-bis ^5-cyclopentadiemlcircomo T |4-l, 3-pentadiene;

N-N'-diisopropyl-dimethylguanidinate borane-bis-r dichloride |5-cyclopentadiemlzirconium; N-N'-diisopropyl-dimethylguanidinate borane-bis-q5-cyclopentadienylzirconium dimethyl; N-N'-diisopropyl-dimethylguamdinate borane-bis-p bis-dimethylamide5-cyclopentadienylzirconium;

N-N'-diisopropyl-dimethylguanidinate borane-bis ^s-cyclopentadienylzirconium 2-methyl-1,3-butadiene;

N-N'-diisopropyl-dimethylguanidinate borane-bis-r |5-cyclopentadienylzirconium 2,3-dimethyl-1,3-butadiene;

N-N'-diisopropyl-dimethylguanidinate borane-bis-r |5-cyclopentadienylzirconium 2-N, N-dimethylaminobenzyl;

N-N'-diisopropyl-dimethylguanidinate borane-bis-r |5-cyclopentadienylzirconium allyl; N-N'-diisopropyl-dimethylguanidinate borane-bis-Tf-cyclopentadienylzirconium u4-l, 4-diphenyl-1,3-butadiene;

N-N'-diisopropyl-dimethylguanidinate borane-bis-p5-cyclopentadienylzirconium r |4-2,4-hexadiene;

N-N'-diisopropyl-dimethylguanidinate borane-bis-p'-cyclopentadicnylzirconium -ri4-l, 4-dinaphthyl1,3-butadiene;

N-N'-diisopropyl-dimethylguanidinate borane-bis ^5-cyclopentadienylzirconium r |4-l-phenyl-1,3-pentadiene;

N-N'-diisopropyl-dimethylguanidinate borane-bis-T)5-cyclopentadiemlzirconium rf-1, 3-pentadiene;

l, 3,4,6,7,8-hexahydro-pyrimido [1,2-a] pyrimidinate borane-bis ^ dichloride5-inden-l-ilzirconium;

1.3.4.6.7.8- hexahydro-pyrimido [1,2-a) pyrimidinate borane-bi su5-inden-1 -ylzirconium dimethyl; l, 3,4,6,7,8-hexahydro-pyrimido [1,2-a] pyrimidinate borane-bis-q bis-dimethylamide5-inden1-ilzirconium;

1.3.4.6.7.8- hexahydro-pyrimido [1,2-a | pyrimidinate borane-bis-tf-inden-l-ylzirconium 2-methyl1,3-butadiene;

1.3.4.6.7.8- hexahydro-pyrimido [1,2-a] pyrimidinate borane-bis-r |5-inden-l-ylzirconium 2,3-dimethyl-1,3-butadiene;

IS 2 188 235 T3

1.3.4.6.7.8- hexahydro-pyrimido [1,2-a] pyrimidinate borane-bis-T)5-inden-l-ylzircomo 2-N, N-dimethylaminobenzyl;

1.3.4.6.7.8- hexahydro-pyrimido [1,2-a] pyrimidinatoborane-bis-T |5-inden-l-üzirconium allyl; lA4,6,7,8-hexahydro-pyridium [1,2-a] piiiimdinatoborane-bis-T |5-inden-l-ilcircoiúoT |4-l, 4-diphenyl-1,3-butadiene;

1.3.4.6.7.8- hexahydro-pyrimido [1,2-a] pyrimidinate borane-bis-r |5-inden-l-ilzirconium η4-2.4hexadiene;

1.3.4.6.7.8- hexahydro-pyrimido [1,2-alpyrimidinate borano-bis-η 5-inden-l-ilzirconium η4-1,4dinaphthyl-1,3-butadiene;

1.3.4.6.7.8- hexahydro-pyrimido [1,2-a] pyrimidinate borane-bis-n5-inden-l-ilzirconium η4-1-ίεnyl-l, 3-pentadiene;

1.3.4.6.7.8- hexahydro-pyrimido [1,2-alpyrimidinate borane-bis © -inden-l-ylzirconium η4-1,3pentadiene;

Ν, Ν'-diisopropyl-phenyl-amidinate borane-bis © - (2-methylinden-l-yl) zirconium dichloride;

N, Ν'-diisopropyl-phenyl-amidinate borane-bis © - (2-methylinden-l-yl) zirconium dimethyl; Ν, Ν'-diisopropyl-phenyl-borane-bis © - (2-methylinden-lyl) zirconium bis-dimethylamide;

Ν, Ν'-diisopropyl-phenyl-amidinate borane-bis-η 5- (2-methylinden-l-yl) zirconium 2-methyl-l, 3-butadiene;

Ν, Ν'-diisopropyl-phenyl-amidinate borane-bis © - (2-methylinden-1-yl) zirconium 2,3-dimethyl-1,3-butadiene;

Ν, Ν'-diisopropyl-phenyl-amidinate borane-bis-η 5- (2-methylinden-l-yl) zirconium 2-N, N-dimethylaminobenzyl;

N, Ν'-diisopropyl-phenyl-amidinate borane-bis © - (2-methylinden-l-yl) zirconium allyl; N, N'-diisopropyl-phenyl-amidinatoborane-bis ^5- (2-methylinden-l-yl) zirconk ^4-l, 4-diphenyl-1,3-butadiene;

N, Ν'-diisopropyl-phenyl-borane-bis-η amidinate 5- (2-methylinden-l-yl) zirconium η4-2.44ιβχ3άίβηο; Ν, Ν'-diisopropyl-phenyl-amidinate borane-bis-η5- (2-methylinden-1 -yl) zirconium η4-1,4-dinaphthyl1,3-butadiene;

Ν, Ν1 -diisopropyl-phenyl-amidinate borane-bis © - (2-mctilinden-1 -yl) zirconium η4-1-phenyl-1,3pentadiene;

N, Ν'-diisopropyl-phenyl-amidinate borane-bis-η - (2-methylinden-l-yl) zirconium η -1,3-penladiene;

N, N'-bis-2,6-diisopropylphenyl-phenyl-amidinate borane-bis © - (2-methyl-4-phenylinden-l-yl) zirconium dichloride;

N, N'-bis-2,6-diisopropylphenyl-phenyl-amidinate borane-bis © - (2-methyl-4-phenylinden-1 yl) zirconium dimethyl;

N, N'-bis-2,6-diisopropylphenyl-phenyl-amidinate borane-bis © - (2-methyl-4-phenylinden-1-yl) zirconium bis-dimethylamide;

N, N'-bis-2,6-diisopropylphenyl-phenyl-amidinate borane-bis ^s- (2-methyl-4-phenylinden-lyl) zirconium 2-methyl-1,3-butadiene;

N, N'-bis-2,6-diisopropylphenyl-phenyl-amidinate borane-bis © - (2-methyl-4-phenylinden-1 yl) zirconium 2,3-dimethyl-1,3-butadiene;

IS 2 188 235 T3

- 4U N, N'-bis-2,6-diisopropylphenyl-phenyl-ami dinato ylzirconium 2-N, N-dimethylaminobenzyl;

N, N'-bis-2,6-diisopropylphenyl-phenyl-amidinate ylzirconium allyl;

N, N'-bis-2,6-diisopropylphenyl-phenyl-amidinate ylzirconium r |4-l, 4-diphenyl-1,3-butadiene;

N, N'-bis-2,6-diisopropylphenyl-phenyl-amidinate yljzirconium T ^ -l ^ -hexadiene;

N, N'-bis-2,6-diisopropylphenyl-phenyl-amidinate yljzirconium η4-1,4- <1ίικΑί1-1,3- ^ Ιη <1ί6ηο;

N, N'-bis-2,6-diisopropylphenyl-phenyl-amidinate yljzirconium η4-1-phenyl-1,3-pentadiene;

N, N'-bis-2,6-diisopropylphenyl-phenyl-amidinate ylzirconium u4-l, 3-pentadiene;

borano-bis-r |5- (2-methyl-4-phenylinden-1 borane-bis-r |5- (2-mctyl-4-phenylinden-lborane-bis-T |5- (2-methyl-4-phenylinden-lborane-bis ^5- (2-methyl-4-phenylinden-lborane-bis-η 5- (2-methyl-4-phenylinden-1 borane-bis-η s- (2-methiI-4-phenylinden-1 borane-bis-η 5- (2-methyl-4-phenylinden-1 dichloride of N, N'-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis-r |5- (2-methyl-4-phenylinden-1-yljzirconium;

N, N'-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis-r |5- (2-methyl-4-phenylinden-liljzirconium dimethyl;

N, N'-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis® - (2-methyl-4-phenylinden-1-yl-zirconium bis-dimethylamide;

N, N'-bis-2,6-diisopropylphenyl-3-methyl-1,3-dichotimine borane-bis-T |5- (2-methyl-4-phenylinden-1 ylzirconium 2-methyl-1,3-butadiene;

N, N'-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis-T |5- (2-methyl-4-phenylinden-liljzirconium 2,3-dimethyl-1,3-butadiene;

N, N'-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis ^5- (2-methyl-4-phenylinden-liljzirconium 2-N, N-dimethylaminobenzyl;

N, N'-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis © - (2-methyl-4-pheiiilinden-1 yljzirconium allyl;

N, N,-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis-r |5- (2-Inethyl-4-phenylinden-liljzirconium T]4-l, 4-diphenyl-1,3-butadiene;

N, N'-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis-r |5- (2-methyl-4-phenylinden-liljzirconium p4-2,4-hexadiene;

N, N'-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis-T |S- (2-methiI-4-phenylinden-liljzirconium Ti4-l, 4-dinaphthyl-l, 3-butadiene;

N, N'-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis-η5- (2-methyl-4-phenylinden-liljzirconium η4-1-ίβπΐ1-1,3-ρβηΐ3 (1ϊεηο;

N, N'-bis-2,6-diisopropylphenyl-3-methyl-l, 3- <lycethymine borane-bis-η5- (2-methyl-4-phenylinden-liljzirconium η4-1,3-pentadiene;

bis (N, N'-diisopropyl-phenyl-amidinate) diborane-1,2-bis © - (2-methyl-4-pheiiilindenl-yl) zirconium dichloride;

bis (N, N,-diisopropyl-phenyl-amidinate) diborane-1,2-bis ^5- (2-methyl-4-phenylinden-l-yl) zirconium dimethyl;

ES 2 188 235 T3 bis-dimethylamide of bis (N, N'-diisopropyl-phenyl-amidinate) diborane-1,2-bis ^3- (2-methyl-4-phenylinden-1-yl) zirconium;

bis (N, N'-diisopropyl-phenyl-amidinate) diborane-1,2-bis-r |5- (2-methyl-4-phenylinden-l-yl) zirconium 2-methyl-1,3-butadiene;

bis (N, N,-diisopropyl-phenyl-ainidinate) diborane-1,2-bis-ps- (2-methyl-4-femlinden-l-yl) zirconium

2,3-dimethyl-1,3-butadiene;

bis (N, N * -diisopropyl-phenyl-amidinate) diborane-1,2-bis-n5- (2-methyl-4-phenylinden-l-yl) zirconium

2-N, N-dimethylaminobenzyl;

bis (N, N'-diisopropyl-phenyl-amidinate) diborane-1,2-bis ^5- (2-methyl-4-phenylinden-1-yl) allyl zirconium;

bis (N, N,-diisopropyl-phenyl-aniidinate) diborane-1,2-bis-r |5- (2-n'yethyl-4-femlinden-l-yl) zircomo η4-1,4-diphenyl-1,3-butadiene;

bis (N, N'-diisopropyl-phenyl-amidinate) diborane-1,2-bis-n5- (2-methyl-4-fcnilinden-l-yl) zirconium p4-2,4-hcxadiene;

bis (N, N,-diisopropyl-phenyl-aniidinate) diborane-1,2-bis-T |5- (2-methyl-4-phenylinden-l-yl) zirconium® l, 4-dinaphthyl-l, 3-butadiene;

bis (N, N'-diisopropyl-phenyl-amidinate) diborane-1,2-bis-p5- (2-methyl-4-phenylinden-1-yl) zirconium η4- 1-phenyl-1,3-pentadiene;

bis (N, N'-diisopropyl-phenyl-amidinate) diborane-1,2-bis-q5- (2-methyl-4-phenylinden-1-yl) zirconium ri4-l, 3-pentadiene;

bis (N, N'-diisopropyl-3-phenyl-l, 3-diketimine) borane-l, 2-bis-p dichloride5- (2-methyl-4-phenylinden-1-yl) zirconium;

bis (N, N'-diisopropyl-3-phenyl-l, 3-diketimine) borane-l, 2-bis ^5- (2-methyl-4-femlinden-lyl) zirconium dimethyl;

bis (N, N'-diisopropyl-3-phenyl-l, 3-diketimine) borane-l, 2-bis-p bis-dimethylamide5- {2-methyl · 4-phenylinden-l -yl) zirconium;

bis (N, N'-diisopropyl-3-phenyl-l, 3-diketimine) borane-l, 2-bis-r |5- (2-methyl-4-phenyinden-lyl) zirconium 2-methyl-1,3-butadiene;

bis (N>N'-diisopropyl-3-phenyl-l, 3-diketimine) borane-l>2-bis-p5- (2-methyl-4-phenylinden-lyl) zirconium 2,3-dimethyl-1,3-butadiene;

bis (N, N'-diisopropyl-3-phenyl-l, 3-diketimma) borane-l, 2-bis-r |S- (2-methyl-4-phenylinden-lyl) zirconium 2-N, N-dimethylaminobenzyl;

bis (N, N'-diisopropyl-3-phenyl-l, 3-diketimine) borane-l, 2-bis ^5- (2-methyl-4-phenylinden-lyl) allyl zirconium;

bis (N, N'-diisopropyl-3-phenyl-l, 3-diketimine) borane-l, 2-bis-r |5- (2-methyl-4-phenylinden-lyl) zirconium r |4-l, 4-diphenyl-1,3-butadiene;

bis (N, N'-diisopropyl-3-phenyl-1,3-dichotimine) borane-1,2-bis-ij 5- (2-methiI-4-phenylinden-1 yl) zirconium p4-2,4-hexadiene;

bis (N, N'-diisopropyl-3-phenyl-1,3-diketimine) borane-1,2-bis ^5- (2-methyl-4-phenylinden-1 yl) zirconium p4-l, 4-dinaphthyl-l, 3-butadiene;

bis (N, N'-diisopropyl-3-phenyl-1,3-dimetimine) borane-1,2-bis ^ 5- (2-methyl-4-phenylinden-1 yl) zirconium p4-l-phenyl-1,3-pentadiene;

ES 2 188 235 T3 bis (N, N'-diisopropyl-3-phenyl-1,3-dicetimine) borane-1,2-bis-r | 5- (2-methyl-4-phenyl nden-1 yl) zirconium η4-1,3-pentadiene;

Ν, Ν'-diisopropyl-phenyl-amidinate borane-bis-η dichloride s- (2-methyl-4-naphthylinden-lyl) zirconium;

Ν, Ν'-diisopropyl-phenyl-amidinate borane-bis-r |5- (2-methyl-4-iiaphthylinden-l-yl) zirconium dimethyl; N.N'-diisopropyl-phenyl-borane-bis-r bis-dimethylamide |5- (2-methyl-4-naphthylinden-lyl) zirconium;

Ν, Ν'-diisopropyl-phenyl-amidinate borane-bis ^5- (2-methyl-4-naphthylinden-l-yl) zircomo 2-methyl1.3-butadiene;

Ν, Ν'-diisopropyl-phenyl-amidinate borane-bis-η 5- (2-methyl-4-naphthylinden-1-yl) zirconium 2,3-dimethyl-1,3-butadiene;

Ν, Ν'-diisopropyl-phenyl-amidinate borane-bis-r |5- (2-methyl-4-naphthylinden-l-yl) zirconium 2-N, N-dimethylaminobenzyl;

Ν, Ν'-diisopropyl-phenyl-amidinate borane-bis-η 5- (2-methyl-4-naphthylinden-1-yl) allyl zirconium; Ν, Ν'-diisopropyl-phenyl-amidinate borane-bis © - (2-methyl-4-naphthylinden-l-yl) zirconium η4-1,4-diphenyl-1,3-butadiene;

Ν, Ν'-diisopropyl-phenyl-amidinate borane-bis ^5- (2-methyl-4-naphthylinden-1-yl) zirconium η4-2.4hexadiene;

Ν, Ν'-diisopropyl-phenyl-amidinate borane-bis-T)5- (2-methyl-4-naphthylinden-1-yl) zirconium η4-1,4dinaphthyl-1,3-butadiene;

Ν, Ν'-diisopropyl-phenyl-amidinate borane-bis © - (2-methyl-4-naphthylinden-l -yl) zirconium η4-1-phenyl-1,3-pentadiene;

Ν, Ν'-diisopropyl-phenyl-amidinate borane-bis-η 5- (2-methyl-4-naphthylinden-l-yl) zirconium η4-1,3pentadiene;

N, N'-diisopropyl-3-phenyl-1,3-diketimine borane-bis-r dichloride |5- (2-methyl-4-naphthylinden-lyl) zirconium;

N, N'-diisopropyl-3-phenyl-1,3-dichotimine borane-bis-η 5- (2-methyl-4-naphthylinden-1-yl) zirconium dimethyl;

bis-dimethylamide of N, N'-diisopropyl-3-phenyl-1,3-diketymia borane-bis-T]5- (2-methyl-4-nanylinden-1-yl) zirconium;

N, N'-diisopropyl-3-phenyl-l, 3-diketimine borane-bis ^5- (2-methyl-4-naphthylinden-l-yl) zircomo 2-methyl-1,3-butadiene;

N, N'-diisopropyl-3-phenyl-1,3-dichotimine borane-bis-η 5- (2-methyl-4-naphthylinden-1-yl) zirconium

2.3-dimethyl-1,3-butadiene;

N, N'-diisopropyl-3-phenyl-1,3-diketimine borane-bis © - (2-methyl-4-naphthylinden-l-yl) zirconium 2N, N-dimethylaminobenzyl;

N, N'-diisopropyl-3-phenyl-1,3-diketimineborane-bis-n5- (2-methyl-4-naphthylinden-l-yl) zirconioalyl;

N, N'-diisopropyl-3-phenyl-1,3-dicetimine borane-bis ^5- (2-methyl-4-naphthylinden-1-yl) zirconium η41,4-diphenyl-1,3-butadiene;

N, N'-diisopropyl-3-phenyl-l, 3-diketimineborane-bis ^5- (2-methyl-4-naphylinden-l-yl) zirconk ^42.4- hexadiene;

IS 2 188 235 T3

N, N'-düsopropyl-3-phenyl-1,3-diketimineborane-bis-Ti5- (2-Inethyl-4-naphthylinden-l-yl) zirconiOT |41,4-dinaphthyl-1,3-butadiene;

N, N'-diisopropyl-3-phenyl-1,3-dichotimine borane-bis-r |5- (2-methyl-4-naphthylinden-1-yl) zirconium η41 -phenyl-1,3-pentadiene;

N, N'-diisopropyl-3-phenyl-1,3-diketimineborane-bis-Ti5- (2-methyl-4-naft¡linden-l-yl) zirconium |41.3- pentadiene;

bis-2,6-diisopropylphenylamido-bis (N, N'-diisopropyl-phenyl-amidinate) diborane titanium dichloride;

bis-2,6-diisopropylphenylamido-bis (N, N'-diisopropyl-phenyl-amidinate) diborane titanium dimethyl; bis-2,6-diisopropylphenylamido-bis (N, N,-diisopropyl-phenyl-amidinate) titanium diborane;

bis-2,6-diisopropylphenylamido-bis (N, N'-diisopropyl-phenyl-amidinate) diborane titanium 2-methyl1.3-butadiene;

bis-2,6-diisopropylphenylamido-bis (N, N'-diisopropyl-phenyl-amidinate) diborane titanium 2,3-dimethyl-1,3-butadiene;

bis-2,6-diisopropylphenylamido-bis (N, N'-diisopiOpil-phenyl-amidinate) diborane titanium 2-N, N-dimethylaminobenzyl;

bis-2,6-diisopropylphenylamido-bis (N, N'-diisopropyl-phenyl-amidinate) diborane titanium allyl; bis-2,6-diisopropylphemlamido-bis (N, N'-diisopropyl-phenyl-amidinate) diborane titanium p4-l, 4-diphenyl-1,3-butadiene;

bis-2,6-diisopropylphenylamido-bis (N, N'-diisopropyl-phenyl-amidinate) diborane titanium η4-2.4hexadiene;

bis-2,6-diisopropylphenylamido-bis (N, N'-diisopropyl-phenyl-amidinate) diborane titanium η4-1,4dinalthyl-1,3-butadiene;

bis-2,6-diisopropylphenylamido-bis (N, N,-diisopropyl-feml-amidinate) diborane titanium ifl-phenyl-l, 3-pentadiene;

bis-2,6-diisopropylphenylamido-bis (N, N'-diisopropyl-phenyl-amidinate) diborane titanium η4-1,3pentadiene;

bis-2,6-diisopropylphenylamido-bis (N, N'-diisopropyl-3-phenyl-1,3-diketimine) diborane titanium dichloride;

bis-2,6-diisopropylphenylamido-bis (N, N'-diisopropyl-3-phenyl-1,3-diketimine) diborane titanium dimethyl;

bis-2,6-diisopropylphenylamido-bis (N, N'-diisopropyl-3-pheny] -l, 3-diketimine) diborane titanium bis-dimethylamide;

bis-2,6-diisopropylphenylamido-bis (N, N'-diisopropyl-3-phenyl-1,3-diketimine) diborane titanium 2-methyl-1,3-butadiene;

bis-2,6-diisopropylphenylamido-bis (N, N'-diisopropyl-3-phenyl-1,3-diketimine) diborane titanium

2.3-dimethyl-1,3-butadiene;

bis-2,6-diisopropylphenylamido-bis (N, N'-diisopropyl-3-phenyl-1,3-diketimine) diborane titanium 2N, N-dimethylaminobenzyl;

bis-2,6-diisopropylphenylamido-bis (N, N'-diisopropyl-3-phenyl-1,3-diketimine) diborane titanium allyl;

bis-2,6-diisopropylphenylamido-bis (N, N'-diisopropyl-3-phenyl-1,3-diketimine) diborane titanium η41,4-diphenyl-1,3-butadiene;

ES 2 188 235 T3 bis-2,6-diisopropylphenylamtdo-bis (N, N'-diisopropyl-3-phenyl-1,3-dicetimine) diborane titanium η4·

2.4- hexadiene;

bis-2,6-diisopropylphenylamido-bis (N, N'-diisopropyl-3-phenyl-1,3-diketimine) diborane titanium η4.

1,4-dinaphthyl-1,3-butadiene;

bis-2,6-diisopropylphenylamido-bis (N, N,-diisopropyl-3-phenyl-l, 3-diketimine) diborane titanium η4. 1-phenyl-1,3-pentadiene; and bis-2,6-diisopropylphenylamido-bis (N, N,-diisopropyl-3-phenyl-1,3-diketimine) diborane titanium η4.

1,3-pentadiene.

One of ordinary skill in the art will recognize that additional members from the above list are also included within the invention, such as those in which boron is replaced by aluminum. Furthermore, it will also be recognized that it is possible that the terms η5 or η4 do not accurately reflect the actual electronic distribution of the molecule under the conditions of use, and it is also intended to include within such descriptions molecules that include lower numbers of atoms that contribute to electronic delocalization.

The most preferred metal complexes for use in this invention are:

dimethylamidoborane-bis (n5-cyclopentadienyl) zirconium; dimethylamidoboranobis dichloride (n5-inden-l-yl) zirconium, dimethylamidoborane-bis (Tf-2-methyl-4-fcnilinden-l-yl) dichloride, dimethylamidoborane-bis ^ dichloride5-2-ethyl-4-femlinden-l-yl) zirconium, dimethylamidoborane-bis- (© 2-isopropyl-4-phenylinden-l-yl) zirconium dichloride, dimethylamidoborane-bis (r |5-2methü-4-bis (3,5-trifluoromethyl) fenUinden-l-yl) zirconium, dimethylamidoborane-bis (n5-3-tbutilinden-1-yl) zirconium, diisopropylamidoborane-bis (T |5-cyclopentadienyl) zirconium, diispropylamidoboranobis (p -inden-l-yl) zirconium dichloride, diisopropylamidoborane-bis dichloride ^5-2-methyl-4-phenylinden-l-yl) zircon, düsopropylamidoborane-bis ^ dichloride5-2-ethiM-phenylinden-l-yl) zirconium, düsopropylamidoborane-bis (n5-2-isopropyl-4-phenibniden-l-yl) zirconium, diisopropylaneudoborane-b¡s (Ti5-2-methyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium; diisopropylamidoborane-bis (Ti5-3-t-butylinden-l-yl) zirconium;

diphenylamidoborane-bis dichloride ^5-cyclopentadienyl) zirconium, diphenylamidoboranobis (r | -inden-l-yl) zirconium dichloride, diphenylamidoborane-bis (T,5-2-methyl-4-phenylinden-lyl) zirconium, diphenylamidoborane-bis ^ dichloride5-2-ethyl-4-femlinden-l-yl) zirconium, diphenylamidoborane-bis (T |5-2-isopropyl-4-phenylinden-l-yl) zirconium, diphenylamidoboranobis (n5-2-methyl-4-bis (3,5-triyluoromethyl) phenylinden-l-yl) zirconium, diphenylamidoboranobis dichloride (ri5-3-t-butylinden-l -yl) zirconium, dimethylanudoborane-bis (T |5-cyclopentadienyl) zirconium 1,4-diphenyl-l, 3-butadiene, dimethylamidoboranobis (r)5-inden-l-yl) zirconium 1,4-diphenyl-l, 3-butadiene, dimethylamidoborane-bisra5-2-methyl-4-phenylinden-lyl) zirconium 1,4-diphenyl-l, 3-butadiene, dimethylamidoborane-bis (r | -2-ethyl-4-phenylinden-l-yl) zirconium 1,4-diphenyl- l, 3-butadiene, dimethylamidoborane-bis (r |s2-isopropyl-4-phenylinden-l-yl) zirconium 1,4-diphenyl-l, 3-butadiene, dimethylamidoborane-bis (r |5-2-methyMbis (3,5-trifluoromethylXenilinden-l-yl) zirconium 1,4-diphenyl-l, 3-butadiene, dimethylamidoborane-bis (T |5-3t-butylinden-l-yl) zirconium 1,4-diphenyl-l, 3-butadiene, diisopropylamidoborane-bis (n5-cyclopentadieml) zirconium 1,4-diphenyl-l, 3-butadiene, diisopropylamidoboranobisOt -inden-l-yl) zirconium 1,4-diphenyl-l, 3-butadiene, diisopropylamidoborane-bis (r |5-2methyl-4-phenylinden-l-yl) zirconium 1,4-diphenyl-l, 3-butadiene, diisopropylamidoborane-bis (n5-2-ethyl-445

ES 2 188 235 T3 phenylinden-1-yl) zirconium 1,4-diphenyl-1,3-butadiene, diisopropylamidoborane-bis (q5-2-isopropyl-4-phenylinden-l-yl) zirconium 1,4-diphenyl-l, 3-butadiene, diisopropylamidoborane-bis (r |5-2-methyl-4-bis (3,5-trifluoromethyl) phenylinden-l-yl) zirconium 1,4-diphenyl-l, 3-butadiene, diisopropylamidoborane-bis (q5-3-tbutilinden-l-yl) zirconium 1,4-diphenyl-l, 3-butadiene, diphenylamidoborane-bis (T]5-cyclopentadienyl) zirconium 1,4-diphenyl-l, 3-butadiene, diphenylamidoboranobis (q5-inden-l-yl) zirconium 1,4-diphenyl-l, 3-butadiene, diphenylainidoborane-bis (p5-2-methyl-4-femlinden-1-yl) zirconium 1,4-diphenyl-l, 3-butadiene, diphenylamidoborane-bis ^5-2-ethyl-4-phenylinden-l yl) zirconium 1,4-diphenyl-1,3-butadiene, diphenylamidoborane-bis ^5-2-isopropyl-4-phenylinden-l -yl) zirconium

1,4-diphenyl-1,3-butadiene, diphenylamidoborane-bis (q5-2-Inethyl-4-bis (3,5-trifluoromethyl) phenylinden-1 yl) zirconium 1,4-diphenyl-l, 3-butadiene, diphenylamidoborane-bis ^5-3-t-butylinden-l-yl) zirconium 1,4-diphenyl-1,3-butadiene.

In general, the complexes of the present invention can be prepared by first converting the ligands depicted in formulas 1a and 2a into a dianionic salt (where R4 is H) by reaction with an alkyl lithium, Grignard reagent, or alkali metal hydride such as NaH or KH. The dianioon ligand derivative is then reacted with a metal complex precursor such as MY3 4, MY33 oMY3 2 (and the corresponding Lewis base adducts), where Y3 it is as defined above. Alternatively, reactions employing the neutral ligand can be employed, where R4 is hydrogen, in combination with the metalic precursors M (NR32) 4 oMR3 4. These reactions are carried out in an inert solvent such as a hydrocarbon solvent or an ethereal solvent in the temperature range of -100 ° C to 150 ° C.

An especially useful metal complex precursor reagent corresponds to formula 3:

where M is zirconium, R1 and LB are as previously defined and Y3 in each case it is chloride. The use of this precursor in the reaction with ligands of this invention makes the resulting metal complex have a high rachoemic purity, which is especially useful in the stereospecific polymerization of α-olefins.

Alternatively, when R4 In structures of formula 1a and 2a is a trimethylsilyl group, the ligand can be reacted directly with any of the above metal complex precursors of formula 3, employing similar reaction conditions.

Recovery of the desired Group 4 transition metal complex is achieved by separating the product from any alkali or alkaline earth metal salts and devolatilizing the reaction medium. If desired, extraction in a secondary solvent can be employed. Alternatively, if the desired product is an insoluble precipitate, filtration or other separation techniques may be employed. Final purification, if required, can be done by recrystallization from an inert solvent, employing low temperatures if necessary.

The complexes become catalytically active through combination with activation cocatalysts or the use of activation techniques that are previously known in the art for use with Group 4 metal complexes for olefin polymerization. Suitable activating cocatalysts for use in this invention include polymeric or oligomoeric alumoxanes, especially methylalumoxane, triisobutyl aluminum modified methylalumoxane, or isobutylalumoxane; Neutral Lewis acids, such as C1-30 hydrocarbyl substituted Group 13 compounds, especially tri (hydrocarbyl) aluminum- or tri (hydrocarbyl) boron compounds and halogenated derivatives (including perhalogen46

ES 2 188 235 T3 two) thereof, having 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially perfluorinated tri (aryl) boron compounds, and even more especially tris (pentafluorophenyl) borane; non-coordinating, compatible, non-polymeric ion-forming compounds (including the use of such compounds under oxidation conditions), especially the use of ammonium, phosphonium, oxonium, carbonium, silyl or sulfonium salts of compatible non-coordinating anions, or salts of ferrocene of non-coordinating compatible anions; mass electrolysis (explained in more detail later); and combinations of the activating cocatalysts and the above techniques. The above activation cocatalysts and activation techniques have been previously taught in relation to different metal complexes in the following references: EP-A-277,003, US-A-5,153,157, US-A-5,064,802, US-A-5,064,802. A-5,321,106, US-A-5,721,185, US-A-5,350,723, US-A-5,425,872, US-A-5,625,087, US-A-5,883,204, USA-5,919,983, US-A-5,783,512, WO 99/15534 and USSN 09 / 251,664, filed February 17, 1999.

Especially desirable activating cocatalysts are combinations of neutral Lewis acids, especially the combination of a trialkylaluminum compound having 1 to 4 carbons in each alkyl group and a halogenated tri (hydrocarbyl) boron compound having 1 to 20 carbons in it. each hydrocarbyl group, especially tris (pentafluorophenyl) borane, additional combinations of such mixtures of neutral Lewis acids with a polymeric or oligomeric alumoxane, and combinations of a single neutral Lewis acid, especially tris (pentafluorophenyl) borane with a polymeric or oligomeric alumoxane. Preferred molar ratios of Group 4 metal complex: tris (pentafluorophenylborane: alumoxane are 1: 1: 1 to 1:10:30, more preferably 1: 1: 1.5 to 1: 5: 10.

Suitable ion-forming compounds useful as cocatalysts in one embodiment of the present invention comprise a cation that is a Bronsted acid capable of donating a proton, and a non-coordinating compatible anion, A-. As used herein, the term "non-coordinating" means an anion or substance that does not coordinate with the precursor complex containing a Group 4 metal and the catalytic derivative obtained therefrom, or that only weakly coordinates with such complexes, thereby remaining labile enough to be displaced by a neutral Lewis base. A non-coordinating anioan specifically refers to an anioan that when functioning as a charge balancing anion in a cationic metal complex does not transfer an anionic substituent or a fragment thereof to said cation, thereby forming neutral complexes. "Compatible anions" are anions that do not degrade to neutrality when the initially formed complex decomposes and that do not interfere with the subsequent desired polymerization or other uses of the complex.

Preferred anions are those that contain a single coordination complex comprising a metal or metalloid nucleus that carries charge, anion that is capable of balancing the charge of the active catalyst species (the metal cation) that can be formed when the two are combined. components. Furthermore, said anion must be sufficiently labile to be displaced by olephane, diolephane and acetylaenically unsaturated compounds or other neutral Lewis bases such as ethers or nitriles. Suitable metals include, but are not limited to, aluminum, gold, and platinum. Suitable metalloids include, but are not limited to, boron, phosphorus, and silicon. Of course, compounds containing anions comprising coordination complexes containing a single metal or metalloid atom are well known, and many, particularly compounds containing a saline boron atom in the portion of the anion, are commercially available. .

Preferably, such cocatalysts can be represented by the following general formula:

(L * -H) d + (A)d- in which:

L* is a neutral Lewis base;

(L*-H)+ is a Bronsted acid conjugated to L*;

TOd- is a non-coordinating, compatible anion having a charge of d-, and integer desunnumer from 1 to 3.

More preferably, Ad- corresponds to the faormula: [M'Q4]- ; in which:

IS 2 188 235 T3

M 'is boron or aluminum in the +3 formal oxidation state; Y

Q independently in each case is selected from hydride, dialkylamido, halide, hydrocarbyl, hydrocarbyl oxide, halo-substituted hydrocarbyl, halo-substituted hydrocarbyloxy and halo-substituted silylhydrocarbyl radicals (including hydrocarbyloxyperhalogenated hydrocarbyl-perhalogenated radicals and silylhydrocarbyl having perhalogenated up to 20 carbons, provided that Q is not halide in more than one case. Examples of suitable hydrocarbyl oxide groups Q are described in US Patent 5,296,433.

In a more preferred embodiment, d is one, that is, the counter has a single negative charge and is A-. The boron-comprising activating cocatalysts that are particularly useful in preparing the catalysts of this invention can be represented by the following general formula:

(L * -H) + (BQ4)-;

in which:

L * is as previously defined;

B is boron in a formal oxidation state of 3; Y

Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl, fluorinated hydrocarbyloxy, or fluorinated silylhydrocarbyl group of up to 20 atoms other than hydrogen, provided that Q is not hydrocarbyl more than once.

Preferred Lewis base salts are ammonium salts, more preferably trialkylammonium salts containing one or more C12-40 alkyl groups. More preferably, Q is in each case 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 tri-substituted ammonium salts such as:

trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluoro) borate, triofenyl (pentafluoro) borate ammonium, N, N-dimethylanilinium tetrakis (pentaylluorophenyl) borate, NN-dimethylanilinium n-butyl (pentafiuorophenyl) borate, NN-dimethylanilinium benzyltris (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4- {t-butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl) borate, N tetrakis (4- (triisopropylsilyl) -2,3,5,6, -tetrafluorophenyl) borate N, N-dimethylanilinium, N-dimethylanilinium, pentafluorophenoxytris (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate,

ES 2 188 235 T3 N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (pentafluorophenyl) borate, dimethyltetradecylammonium tetrakis (pentafluorophenyl) borate, dimethylhexadecylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, dimethylhexadecylammonium tetrakis (dimethyl) bontazimmonium tetrakis (dimethyl) boratemonium tetrakis (pentafluorophenyl) borate (pentafluorophenyl) methylditetradecylammonium borate, (hydroxyphenyl) tris (pentafluorophenyl) methylditetradecylammonium borate, (diethylaluminoxyphenyl) tris (pentafluorophenyl) methylditetradecylammonium borate, tetrakis (pentafluorophenyl) borate metildihexadecilamonio, (hydroxyphenyl) tris (pentafluorophenyl) borate metildihexadecilamonio, (dietilaluminoxifenil) tris (pentafluorophenyl) borate metildihexadecilamonio tetrakis (pentafluorophenyl) borate methyldioctadecylammonium (hydroxyphenyl) tris (pentafluorophenyl) borate methyldioctadecylammonium ( methyldioctadecylammonium diethylaluminoxyphenyl) tris (pentaylluorophenyl) borate, mixtures of the above, dialkylammonium salts such as: di- (i-propyl) ammonium tetrakis (pentafluorophenyl) borate, methyloctadecylammonium tetrakis (pentafluorofeml) borate, methyloctedecylammonium tetrakis (pentafluorophenyl) borate, and tetrakis (pentafluorophenyl) borate (substituted dioctadecylammonium phosphonium salts such as tetrakis: phosphoxylammonium tetrakis) triphenylphosphonium pentafluorophenyl) borate, methyldioctadecylphosphonium tetrakis (pentafluorophenyl) borate and tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate; di-substituted oxonium salts such as: diphenyloxonium tetrakis (pentafluorophenyl) borate, di (o-tolyl) oxonium tetrakis (pentafluorophenyl) borate and di (octadecyl) oxonium tetrakis (pentafluorophenyl) borate, di-substituted sulfonium salts such as: di (o-tolyl) sulfonium tetrakis (pentafluorophenyl) borate and methyloctadecylsulfonium tetrakis (pentafluorophenyl) borate.

They are cations (L* -H)+ preferred methyldioctadecylammonium and dimethyloctadecylammonium.

Another suitable ion-forming activating cocatalyst comprises a salt of a cationic oxidation agent and a non-coordinating compatible anion represented by the formula:

(Oxe +)givesd-) in which:

Oxe + it is a cationic oxidizing agent that has a charge of e +; e is an integer from 1 to 3; alreadyd- and d are as previously defined.

Examples of cationic oxidizing agents include: ferrocenium, hydrocarbyl substituted ferrocenium, Ag+ or Pb+2. Preferred embodiments of Ad- the anions previously defined with respect to the Bronsted acid-containing activating cocatalysts, especially tetrakis (pentafluorophenyl) borate.

IS 2 188 235 T3

Another suitable ion-forming activating cocatalyst comprises a compound that is a salt of a carbenium ion and a non-coordinating compatible anion represented by the formula:

TO- it is as previously defined. A preferred carbenium ion is the trityl cation, which is triphenylmethylium.

Another suitable ion-forming activating cocatalyst comprises a compound which is a salt of a silylium ion and a non-coordinating compatible anion represented by the formula:

R3Si (X ') q+TO- in which:

R is C1-10 hydrocarbyl, yX ', qyA- they are as previously defined.

Preferred silylium salt activating cocatalysts are trimethylsilyl tetrakispentafluorophenylborate, triethylsilylium 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 in Lambert, JB, et al., Organometallics, 1994, 13, 2430-2443. In US Serial Number 304,314, filed September 12, 1994, equivalently published as WO 96/08519 on March 21, 1996, the use of the above silyllium salts as activating cocatalysts for additional polymerization catalysts.

Certain complexes of alcohols, mercaptans, silanols and oximes with tris (pentafluorophenyl) borane are also effective catalyst activators and can be used in accordance with the present invention. Such cocatalysts are described in USP 5,296,433.

Another class of suitable catalyst activators includes anioonic compounds corresponding to the formula:

(TO1 + a1) b1 (Z1Jj11) -c1d1, in which:

TO1 is a charge cation + a1 ,

Z1 is an anionic group of 1 to 50, preferably 1 to 30 atoms, not counting hydrogen atoms, containing in addition two or more Lewis base sites;

J1 , independently in each case, is a Lewis acid coordinated with at least one Lewis base site of Z1 , and optionally two or more of such groups J1 can be joined together to form a moiety that has multiple Lewis acid functionality, j1 is a number from 2 to 12 and1, b1, c1 and d1 are integer numbers from 1 to 3, with the condition that a1 xb1 be equal to c1 XD1 .

The above cocatalysts (illustrated by those having imidazolide, substituted imidazolid, imidazolinide, substituted imidazolinide, benzimidazolide or substituted benzimidazolide anions) can be represented schematically as follows:

IS 2 188 235 T3

where:

TO1+ is a monovalent cation as previously defined, and is preferably a trihydrocarbyl ammonium cation, containing one or two C10-40 alkyl groups, especially methylbis (tetradecyl) ammonium- or methylbis (octadecyl) ammonium- cation,

R8, independently in each case, is hydrogen or a halo, hydrocarbyl, halocarbyl, halohydrocarbyl, silylhydrocarbyl or silyl group (including mono-, di- and tri (hydrocarbyl) silyl) of up to 30 aotoms not counting hydrogens, preferably C1-20 alkyl , Y

J1 it is tris (pentafluorophenyl) borane or tris (pentafluorophenyl) aluminate.

Examples of these catalyst activators include the trihydrocarbylammonium-, especially methylbis (tetradecyl) ammonium- or methylbis (octadecyl) ammonium- salts of:

bis (tris (pentafluorophenyl) borane) imidazolid, bis (tris (pentafluorophenyl) borane) -2-undecylimidazolid, bis (tris (pentafluorophenyl) borane) -2-heptadecylimidazolid, bis (tris (pentafluorophenyl) borane) -4,5-bis (undecyl) imidazolid, bis (tris (pentafluoraphenyl) borane) -4,5-bis (heptadecyl) imidazolid, bis (tris (pentafluorophenyl) borane) -imidazolinide, bis (tris (pentafluoraphenyl) borane) -2-undecylimidazolinide, bis ( tris (pentafluoraphenyl) borane) -2-heptadecylimidazolinide, bis (tris (pentafluorophenyl) borane) -4,5-bis (undecyl) imidazolinide, bis (tris (pentafluorophenyl) borane) -4,5-bis (heptadecyl) imidazolinide, bis (tris (pentafluorophenyl) borane) -5.6 -dimethylbenzimidazolid, bis (tris (pentafluorophenyl) borane) -5,6-bis (undecyl) benzyneidazolid, bis (tris (pentafluorophenyl) aluman) imidazolid, bis (tris (pentafluorophenyl) aluman) -2-undecylimidazolid, bis (tris (tris) ) aluman) -2-heptadecylimidazolid, bis (tris (pentafluorophenyl) aluman) -4,5-bis (iindecyl) iimdazolid, bis (tris (pentafluorophenyl) aluman) -4,5-bis (heptadecyl) imidazolide, bis (tris (pentafluorophenyl) aluman) -imidazolinide, bis (tris (pentafluorophenyl) aluman) -2-undecylimidazolinide, bis (tris (pentafluorofluorofen) ) -2-heptadecylimidazolinide, bis (tris (pentafluorophenyl) aluman) -4,5-bis (undecyl) imidazolinide, bis (tris (pentafluorophenyl) aliunan) -4,5-bis (heptadecyl) imidazolinide, bis (tris (pentafluorophenyl) aluman) -5,6-dimethylbenzimidazolide, and bis (tris (pentafluorophenyl) aluman) -5,6-bis (undecyl) benzimidazolid.

IS 2 188 235 T3

The employed molar ratio of catalyst / cocatalyst preferably ranges from 1: 10,000 to 100: 1, more preferably from 1: 5000 to 10: 1, even more preferably from 1: 1000 to 1: 1. Alumoxane, when used by itself as an activating cocatalyst, is employed in a large amount, generally at least 100 times the amount of metal complex on a molar basis. Tris (pentafluorophenyl) borane, when used as an activating cocatalyst, is used in a molar ratio to metal complex of 0.5: 1 to 10: 1, more preferably 1: 1 to 6: 1 and even more. more preferably 1: 1 to 5: 1. The remaining activating cocatalysts are generally used in a molar ratio to the metal complex of 0.9: 1 to 3: 1, and preferably in an amount approximately equimolar to the metal complex, i.e. 1: 1 to 1, 5: 1.

The catalyst composition can be prepared and employed as a heterogeneous catalyst by adsorption, deposition, or chemical binding of the required components on an inorganic or organic particulate solid. Examples of such solids include salice, salice gel, alumina, clays, expanded clays (aerogels), aluminosilicates, trialkylaluminum compounds, and organic or inorganic polymeric materials, especially polyolefins. In a preferred embodiment, a heterogeneous catalyst is prepared by reacting an inorganic compound, preferably a tri (C1-4alkyl aluminum compound with an activating cocatalyst, especially an ammonium salt of a hydroxyaryl (trispentafluorophenyl) borate, such as a (4-hydroxy-3,5-di-tert-butylphenyl) tris (pentafluorophenyl) borate or (4-hydroxyphenyl) -tris (pentafluorophenyl) borate ammonium salt. This activating cocatalyst is deposited on the support by coprecipitation, impregnation, spraying or a similar technique, and subsequently removing any solvent or diluent. The metal complex is added to the support, also by adsorption, deposition or chemical bonding thereof to the support, subsequently, simultaneously or before the addition of the activating cocatalyst.

The catalysts, preferably supported in any of the above methods, can be used to polymerize ethylanically and / or acetylenically unsaturated monomers having 2 to 8 carbon atoms, alone or in combination, in the gas phase. Preferred monomers include the C2-6 α-olefins, especially ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene,

4-methyl-1-pentene and mixtures thereof. Other preferred monoamers include 1,3-butadiene, ethylidene-bornene, and mixtures thereof. Preferred monoamers include ethylene or a mixture of α-olefins C2-6.

Long chain macromolecular α-olefins are vinyl-terminated polymeric residues formed in situ, especially during continuous or semi-continuous polymerization reactions. Under proper processing conditions, such long chain macromolecular units readily polymerize to provide the polymerase product together with ethylene and other short chain olefin monomers to give small amounts of long chain branches in the resulting polymer. Such polymers possess improved rheological properties, especially better extrusion characteristics compared to polymers containing relatively fewer long chain branches. An analytical measure that can indicate the presence of a long chain branching in an olefin polymer is the presence of a high I10 / I2 value or a high I21 / I2 value, even if it has a narrow molecular weight distribution determined by Mw / Mn (weight average molecular weight / number average molecular weight), compared to polymers that do not have long chain branches. Polymers having a Mw / Mn value of less than 3.5, especially less than 3.0, especially less than 2.8 and an I10 / I2 value of greater than 10, preferably greater than 20 and even more preferably are preferred. over 30.

In general, the polymerization can be carried out under conditions well known in the art for gas phase polymerization reactions, that is, temperatures from 0-250 ° C, preferably 60 to 150 ° C, more preferably 70 to 110 ° C, and pressures from atmospheric to 10,000 atmospheres. A support, especially salice, alumina, or a polymer (especially poly (tetrafluoroethylene) or a polyolefin) may be employed, and is desirably employed to obtain a desired particulate morphology of the polymer. The support is preferably employed in an amount to provide a ratio of catalyst weights (to metal): support of 1: 100,000 to 1:10, more preferably 1: 50,000 to 1:20, and even more preferably 1 : 10,000 to 1:30. In most polymerization reactions, the molar ratio of catalyst: polymerizable compounds used is 10-12: 1a10-1: 1, more preferably 10-9: 1 to 10-5:1.

At all times, the individual ingredients as well as the recovered catalyst components must be protected from oxygen and moisture. Therefore, the catalyst components and catalysts must be prepared and recovered in an oxygen-free and moisture-free atmosphere. Therefore, preferably, the reactions are carried out in the presence of a dry inert gas such as, for example,

ES 2 188 235 T3 nitrogen.

Gas phase processes for olefin polymerization, especially homopolymerization and copolymerization of ethylene and propylene, and copolymerization of ethylene with higher α-olefins are well known in the art. The polymerization can be carried out as a batch or continuous polymerization process. A continuous process is preferred, in which case the catalyst, ethylene, comonoomer, and optionally solvent are supplied continuously to the reaction zone and the polymeric product is continuously or intermittently withdrawn from said zone. The gas phase process employed may be, for example, of the type employing a mechanically stirred bed or a fluidized bed of gas as the polymerization reaction zone. The process in which the polymerization reaction is carried out in a vertical cylindrical polymerization reactor containing a fluidized bed of polymeric particles supported on a preformed plate, the fluidization grid, by a fluidizing gas flow, is preferred.

The cooling of the reactor can be accomplished through the use of recycle gas, which is supplied as a volatile liquid to the bed to provide a cooling effect by vapor formation. The volatile liquid employed in this case can be, for example, an inert volatile liquid, for example a saturated hydrocarbon having 3 to 8, preferably 4 to 6 carbon aotoms. In case the monoomer or comonoomer itself is a volatile liquid (or can be condensed to provide such a liquid), it can be supplied to the bed to provide a vapor-forming cooling effect. The volatile liquid evaporates in the hot fluidized bed to form gas which mixes with the fluidization gas. If the volatile liquid is a monomer or comonoomer, it will undergo some polymerization in the bed. The evaporated liquid then exits the reactor as part of the hot recycle gas, and enters the compression / heat exchange part of the recycle cycle. The recycle gas is cooled in the heat exchanger and, if the temperature to which the gas is cooled is below the dew point, the gas will condense into liquid. This liquid is preferably continuously recycled to the fluidized bed. It is possible to recycle the condensed liquid to the bed in the form of liquid droplets carried in the recycle gas stream. This type of process is described, for example, in documents EP-A-089691; USP 4,543,399; WO 94/25495 and USP 5,352,749. A particularly preferred method of recycling the liquid to the bed is to separate the liquid from the recycle gas stream and reinject this liquid directly into the bed, preferably using a method that generates fine droplets of the liquid within the bed. This type of process is described in WO 94/28032.

The polymer is produced directly in the fluidized bed by catalyzed copolymerization of the monoomer and one or more comonomers on the fluidized particles of the catalyst, supported catalyst, or prepolymer within the bed. Initiation of the polymerization reaction is desirably accomplished by using a bed of preformed polymer particles, which are preferably similar to the desired polyolefin, and conditioning the bed in accordance with techniques that are well known in the art. Such 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 used to fluidize the bed comprises the monomer or monomers to be polymerized, and also serves as a heat exchange medium to remove reaction heat from the bed. The hot gases exit the upper part of the reactor, usually through a quiet zone, also known as the speed reduction zone, which has a greater cross-sectional area than the fluidized bed and in which the fine particles trapped in the gas stream have the opportunity to return to the bed by gravity. It may also be advantageous to use a cycloon to remove fine particles from the hot gas stream. The gas is then normally recycled to the bed by means of a fan or compressor and one or more heat exchangers to remove the heat of polymerization from the gas. The polymer produced is discharged continuously or discontinuously from the fluidized bed, as desired.

Topically, the molar ratio of comonomer to monomer used in polymerization depends on the density desired for the composition to be produced and is desirably about 0.5 or less. Desirably, when materials with a density range of 0.91 to 0.93 are produced, the ratio of comonoomer to monomer is less than 0.2, preferably less than 0.05, even more preferably less than 0.02. and it can even be less than 0.01. Hydrogen can be added to the reaction to control the molecular weight and melt onyx of the polymer. Topically, the hydrogen to monomer ratio is less than about 0.5, preferably less than 0.2, more preferably less than 0.05, and still more preferably less than 0.01.

Several patents and patent applications describe gas phase processes that can be adapted

ES 2 188 235 T3 for use in the process of this invention, particularly USP 4,588,790; 4,543,399; 5,352,749; 5,436,304; 5,405,922; 5,462,999; 5,461,123; 5,453,471; 5,032,562; 5,028,670; 5,473,028; 5,106,804; 5,541,270, EP-A-659,773; EP-A-692,500; WO 94/29032, WO 94/25497, WO 94/25495, WO 94/28032; WO 95/13305; WO 94/26793; and WO 95/07942.

Examples

Those skilled in the art appreciate that the invention described herein can be practiced in the absence of any component not specifically described. The following examples are provided as a further illustration of the invention and are not to be construed as limiting.

Unless otherwise indicated, all parts and percentages are on a weight basis. The term "one night", if used, refers to a time of approximately 16-18 hours, the term "room temperature" refers to a temperature of approximately 20-25 ° C, and the term "mixed alkanes" refers to to a commercially available mixture of C6-8 aliphatic hydrocarbons available under the trade name Isopar E® from Exxon Chemicals Inc.

NMR Spectra 1H (300 MHz) and 13C (75 MHz) were recorded on a Varian XL-300 spectrometer. The NMR spectra of1Hy13C use residual solvent peaks as reference and are reported in ppm with respect to tetramethylsilane. All J values are given in Hz. Tetrahydrofuran (THF), diethyl ether, toluene, and hexane were used after passing through double columns loaded with activated alumina and a purification catalyst (Q-5® available from Englehardt Chemicals Inc. ). Compounds BCl3-SMe2, BBr3-SMe2, B (NMe2) 3, and n-BuLi were used as purchased from Aldrich. Compound Ti Cl3 (THF) 3 was prepared as described in the literature. All prostheses were performed in dry nitrogen or argoon atmospheres using a combination of a glove box and high vacuum techniques.

Example 1

Dichloro- [1,2-bis (2,6-diisopropylanilide) -1,2-bis (dimethylamido) diborane] titanium

1A) Preparation of Chlorobis (dimethylamido) borane, (modification of Chavant, PY; Vaultier, MJ Organomet. Chem. 1993, 455, 37-46)

BCl3-SME2 (62,000g, 345.78mmol) and B (NMe2) 3 (98.921g, 691.56mmol) were stirred together at room temperature overnight under a nitrogen sparger. The mixture was then refluxed for one hour to remove all of the SMe.2 residual. After allowing the pale yellow liquid to stir at room temperature, the desired product was cleanly isolated (yield 44.979 g, 99.9 percent).

1H NMR (C6D6): δ 2.49 (s, 12H). 13C NMR (C6D6): δ 39.86.

IS 2 188 235 T3

IB) Preparation of Tetrakis (dimethylamido) diborane (modification of Noth, H; Meister, WZ Naturforsch. Teil B 1962, 17, 714)

Chlorobis (dimethylamido) borane (30,000 g, 223.19 mmol) in hexane (200 ml) was heated to reflux, followed by adding dropwise a Na / K alloy [Na (1.539 g, 66.96 mmol) / 8.726 g K (8.726 g, 223.19 mmol)] to solution. After the first few drops, the reaction started as demonstrated by a rapid increase in reflux. The heat was then removed and the alloy was added slowly so as to maintain a reflux. After the addition was complete, the reaction mixture was heated under reflux for one more hour and then stirred at room temperature for three hours. The mixture was then filtered through a layer of diatomaceous earth and the volatiles were removed, resulting in the isolation of a yellow liquid. Fractional distillation in vacuo resulted in the isolation of the desired compound as a pale yellow liquid (7.756 g, 35.1 percent yield).

1H NMR (C6D6): δ 2.74 (s, 24H). 13C NMR (C6D6): δ 41.34.

IC) Preparation of bis (dimethylamido) diboro dichloride (modification of Noth, H; Meister, WZ Naturforsch., Teil B 1962, 17, 714).

Tetrakis (dimethylamido) diborane (7.76 g, 39.29 mmol) was stirred in diethyl ether (100 ml) at -78 ° C as HCl (150 mmol, 157 ml of a 1.0 M solution was added dropwise). in diethyl ether). Then, this mixture was allowed to stir for six hours at room temperature. After the reaction period, the volatiles were removed and the residue was removed and filtered using hexane. Removal of the hexane resulted in the isolation of a yellow oil. Fractional distillation in vacuo resulted in the isolation of the desired compound as a pale yellow liquid (4.72 g, 66.7 percent yield).

1H NMR (C6D6): δ 2.40 (s, 6H), 2.50 (s, 6H). 13CRMN (C6D6): δ 37.62, 41.78.

ID) Preparation of 2-6-Diisopropylaniline, lithium salt

N-BuLi (56.4 mmol, 35.3 ml of a 1.60 M solution in hexane) was added dropwise to a solution of 2,6-diisopropylaniline (10.0 g, 56.4 mmol) in hexane (100 ml). This mixture was allowed to stir for 3 hours, during which time a white precipitate formed. After the reaction period, the mixture was filtered and the white salt was washed with hexane, vacuum dried and used without further purification or analysis (9.99 g, 96.7 percent).

IE) Preparation of 1,2-Bis (2,6-diisopropylanilide) -1,2-bis (dimethylamido) diborane

Bis (dimethylamido) diboro dichloride (2.35 g, 13.0 mmol) in diethyl ether (10 ml) was added dropwise to a solution of 2,6-diisopropylaniline, lithium salt (4.77 g, 26 , 0 mmol) in dietary ether (50 ml) at 0°C. The mixture was then left stirring overnight at room temperature. After the reaction period, the volatiles were removed and the residue was removed and filtered using hexane. Removal of the hexane resulted in the isolation of the desired product as a white solid (5.32 g, 88.9 percent yield).

1NMR (C6D6, RT): δ 0.9-1.4 (ma, 24H), 2.3 (s, 6H), 2.8 (s, 6H), 3.7 (s, 2H), 7 , 0 (bs, 6H).

IF) Preparation of 1,2-Bis (2,6-diisopropylanilide) -1,2-bis (dimethylamido) diborane, dilithium salt

1,2-bis (2,6-diisopropylanilide) -1,2-bis (dimethylamido) diborane (1.82 g, 3.95 mmol) in hexane (75 ml) was stirred as added dropwise n -BuLi (7.91 mmol, 4.94 ml of a 1.60 M solution in hexane). This mixture was then stirred overnight. After the reaction period, the mixture was filtered and washed well with hexane and vacuum dried, resulting in isolation of the desired product as a white powder (1.69 g, 90.4 percent yield).

IG) Preparation of Dichloro- [1,2-Bis (2,6-diisopropylanilide) -1,2-bis (dimethylamido) diborane] titanium

1,2-bis (2,6-diisopropylanilide) -1,2-bis (dimethylamido) diborane, dilithium salt (0.60 g, 1.27 mmol) in THF (20 ml) was added dropwise at a suspension of TiCl3 (THF) 3 (0.47 g, 1.27 mmol) in THF (50 ml) a0°C. This mixture was then allowed to stir at room temperature for 45 minutes. Then PbCl was added2 (0.177 g, 0.640 mmol) as a solid and the mixture was allowed to stir for more than 30 minutes. After the reaction period, the volatiles were removed and the residue was removed and

ES 2 188 235 T3 filter using hexane. Concentration of the hexane and refrigeration at -10 ° C overnight resulted in the formation of orange X-ray quality crystals (0.156 g, 21.3 percent yield).

1H NMR (C6D6): δ 1.23 (d, 3JHH = 6.6 Hz, 6H), 1.45 (d, 3JHH = 6.6 Hz, 6H), 2.17 (s, 6H), 2.76 (s, 6H), 3.53 (septet, 3JHH = 6.6 Hz, 4H), 7.11 (s, 6H).

Example 2

Dichloro [1,2-Bis (2,6-diisopropylanilide) -1,2-bis (dimethylamido) diborane] titanium (alternative preparation) 2A) Preparation of Chlorobis (dimethylamido) borane.

BCl3-SMe2 (62,000 g, 345.78 mmol) and B (NMe2) 3 (98.921 g, 691.56 mmol) were stirred together at room temperature overnight under a nitrogen sparger. The mixture was then refluxed for one hour to remove all residual SMe2. By allowing the pale yellow liquid to stir at room temperature, isolation of the desired product occurred (139.436 g, 93.3 percent yield).

1H NMR (C6D6): δ 2.49 (s, 12H). 13C NMR (C6D6): δ 39.86.

2B) Preparation of Tetrakis (dimethylamido) diborane by CIB (NMe)2

Chlorobis (dimethylamido) borane (30,000 g, 223.19 mmol) in hexane (200 ml) was heated to reflux, followed by adding dropwise a Na / K alloy [Na (1.539 g, 66.96 mmol) / 8.726 g K (8.726 g, 223.19 mmol)] to solution. After the first few drops, the reaction will start as demonstrated by a rapid increase in reflux. The heat was then removed and the alloy was slowly added to maintain a reflux. After the addition was complete, the reaction mixture was heated under reflux for an additional hour and then stirred at room temperature for three hours. The mixture will then be filtered through a layer of diatomaceous earth and the volatile components are removed, resulting in the isolation of a yellow liquid. Fractional distillation in vacuo resulted in the isolation of the desired compound as a pale yellow liquid (7.756 g, 35.1 percent yield) 1NMR (C6D6): δ 2.73 (s, 24H). 13CRMN (C6D6): δ 41.37.

2C) Preparation of Tetrakis (dimethylamido) diborane by bis (catecholate) diboron.

Lithium dimethylamide (10.70 g, 210.0 mmol) as a solid was slowly added to a solution of bis (catecholate) diboron (10.00 g, 42.00 mmol) in diethyl ether (200 ml) to -20 ° C. This mixture was then allowed to stir for a further 40 hours at room temperature. After the reaction period, the ether was removed to the vacuum and the residue was removed and filtered using hexane. Removal of the hexane resulted in the isolation of a yellow oil. Fractional distillation in vacuo resulted in the isolation of the desired compound as a pale yellow liquid (5.493 g, 66.0 percent yield).

2D) Preparation of bis (dimethylamido) diboron dichloride

Tetrakis (dimethylamido) diborane (7.756 g, 39.19 mmol) in diethyl ether (100 ml) was stirred at -78 ° C as HCl (156.75 mmol, 156.75 ml of a solution 1, 0 M in diethyl ether). Afterwards, this mixture was left stirring for six hours at room temperature. After the reaction period, the volatile components were removed and the residue was extracted and filtered using hexane. Removal of the hexane resulted in the isolation of a yellow oil. Fractional distillation in vacuo resulted in the isolation of the desired compound as a pale yellow liquid (4.722 g, 66.7 percent yield).

1NMR (C6D6): δ 2.40 (s, 6H), 2.50 (s, 6H). 13CRMN (C6D6): δ 37.62, 41.78.

2E) Preparation of 2,6-Diisopropylaniline, lithium salt

N-BuLi (56.40 g, 35.25 ml of a 1.6 M solution in hexane) is added dropwise to a solution of 2,6-diisopropylaniline (10.00 g, 56.40 mmol) in hexane (100 ml). This mixture was allowed to stir for 3 hours, during which time a white precipitate formed. After the reaction period,

ES 2 188 235 T3 the mixture was filtered and the white salt was washed with hexane, dried in vacuo and used without further purification or analysis (9.988 g, 96.7 percent yield).

2F) Preparation of 1,2-Bis (2,6-diisopropylanilide) -1,2-bis (dimethylamido) diborane

Bis (dimethylamido) diboro dichloride (2.350 g, 13.00 mmol) in diethyl ether (10 ml) was added dropwise to a solution of 2,6-diisopropylaniline, lithium salt (4.765 g, 26.01 mmol) in dietary ether (50 ml) to

0°C. This mixture was then allowed to stir overnight at room temperature. After the reaction period, the volatiles were removed and the residue was removed and filtered using hexane. Removal of the hexane resulted in the isolation of a desired product as a white solid (5.322 g, 88.9 percent yield).

1H NMR (toluene-d8): δ 0.9-1.4 (ma, 24H), 2.3 (s, 6H), 2.8 (s, 6H), 3.7 (s, 2H), 7.0 (brs, 6H). 13C NMR (toluene-d8): δ 22.51, 24.03 (a), 28.17, 36.82, 42.67, 123.19, 124.78, 140.71, 145.02 (a) . MS (EI): m / z 460.4025 (MH)+, calculated (MH)+ 460,4026.

2G) Preparation of 1,2-Bis (2,6-diisopropylanilide) -1,2-bis (dimethylamido) diborane, dilithium salt

1,2-bis (2,6-diisopropylanilide) -1,2-bis (dimethylamido) diborane (1.820 g, 3.950 mmol) was stirred in hexanes (75 ml) as n-BuLi (7.91 mmol, 4.94 ml of a 1.6 M solution in hexane). This mixture was then allowed to stir overnight. After the reaction period, the mixture was filtered and washed well with hexane and vacuum dried, resulting in isolation of the desired product as a white powder (1.6878 g, 90.4 percent yield).

1H NMR (THF-d8): δ 1.04 (d, 3JHH = 6.9 Hz, 6H), 1.18 (d, 3JHH = 6.9 Hz, 6H), 2.45 (s, 12H), 3.66 (septet, 3JHH = 6.9 Hz, 4H), 6.29 (t, 3JHH = 7.5 Hz, 2H), 6.73 (d, 3JHH = 7.5 Hz, 4H). 13CRMN (TH -d8): δ 24.88, 25.34, 28.00, 40.91, 114.40, 121.95, 137.21, 158.76.

2H) Preparation of Dichloro- [1,2-bis (2,6-diisopropylanilide) -1,2-bis (dimethylamido) diborane] titanium

1,2-bis (2,6-diisopropylanylide) -1,2-bis (dimethylamido) diborano, dilithium salt (0.600 g, 1.27 mmol) in THF (20 ml) was added dropwise to a suspension of TiCl3 (THF) 3 (0.471 g, 1.27 mmol) in THF (50 mL) at 0°C. This mixture was then allowed to stir at room temperature for 45 minutes. Then PbCl was added2 (0.177 g, 0.640 mmol) as a solid and the mixture was allowed to stir for more than 30 minutes. After the reaction period, the volatile components were removed and the residue was extracted and filtered using hexane. Concentration of the hexane fractions and cooling to -10°C overnight resulted in the formation of orange X-ray quality crystals (0.156, 21.3 percent yield).

1H NMR (toluene-d8): δ 1.23 (d, 3JHH = 6.6 Hz, 6H), 1.45 (d, 3JHH = 6.6 Hz, 6H), 2.17 (s, 6H), 2.76 (s, 6H), 3.53 (septet, 3JHH = 6.6 Hz, 4H), 7.11 (s, 6H). 13C NMR (toluene-d8): δ 24.94, 24.67, 29.48, 39.33, 42.93, 124.08 (br), 17.23, 150.64. MS (mass spectrum) (EI): m / z 578.2789 (M)+, calculated (M)+ 578.2781. Analysis calculated for C28H46B2N2TiCl2: C, 58.07; H, 8.01; N, 9.67. Found: C, 8.28; H, 8.20; N, 9.42.

Example 3

Dimethyl [1,2-Bis (2,6-diisopropylanilide) -1,2-bis (dimethylamido) diborane] titanium

Dichloro- [1,2-bis (2,6-diisopropylanilide) -1,2-bis (dimethylamido) diborane] titanium (Example 2) (0.272 g, 0.470 mmol) in diethyl ether (40 ml) was stirred as added MeMgBr dropwise (0.940 mmol, 0.313 ml of a 3.0 M solution in diethyl ether). This mixture was allowed to stir for one hour. After the reaction period, the volatiles were removed and the residue was extracted and filtered using hexane. Removal of the hexane resulted in isolation of the desired product as a dark yellow oil (0.209 g, 82.5 percent yield).

1H NMR (C6D6): δ 1.05 (s, 6H), 1.21 (d, 3JHH = 6.9 Hz, 16H), 1.32 (d, 3JHH = 6.3 Hz, 16H), 2.19 (s, 6H), 2.69 (s, 6H), 3.58 (br, 2H), 7.0-7.2 (m, 6H). 13C NMR (C6D6): δ 24.06, 24.83, 29.31, 39.58, 42.93, 57.38, 123.97, 125.18, 139.5 (br), 149.45.

IS 2 188 235 T3

Example 4

Dibenzyl [1,2-Bis (2,6-diisopropylanilide) -1,2-bis (dimethylamido) diborane] zirconium

Zirconium tetrachloride (0.100 g, 0.440 mmol) and tetrabenzyl zirconium (0.192 g, 0.440 mmol) were stirred together in diethyl ether (30 ml) for 1 hour. Then 1,2-bis (2,6-diisopropylanilide) -1,2-bis (dimethylamido) diborane, dilithium salt (Example 2G) (0.400 g, 0.842 mmol) in diethyl ether (30 ml) and the The mixture was allowed to stir for 3 hours. After the reaction period, the volatiles were removed in vacuo and the residue was removed and filtered using hexane. The filtrate was then concentrated and cooled to -10 ° C overnight, during which time a white powder precipitated. The mixture was filtered again and volatile components were removed resulting in isolation of the desired product as a yellow oil (0.123 g, 19.8 percent yield).

1H NMR (toluene-d8): δ 1.14 (d, 3JHH = 6.6 Hz, 6H), 1.22 (a, 6H), 1.70 (d, 3JHH = 9.0 Hz, 2H), 1.83 (d, 3JHH = 9.6Hz, 2H), 2.10 (s, 6H), 2.71 (s, 6H), 3.0-3.2 (a, 2H), 3.3-3.5 (a, 2H), 6.59 (d, 3JHH = 7.2 Hz, 4H), 6.77 (t, 3JHH = 7.2 Hz, 2H), 6.9-7.1 (m, 10H). 13C NMR (toluene-d8): δ 23.96 (a), 24.22 (a), 24.36 (a), 25.23 (a), 29.47, 39.72, 43.05, 62 , 23, 122.70, 123.73 (a), 124.08 (a), 124.33, 127.23, 130.82, 139.26 (a), 140.16 (a), 144.90 , 144.92, 149.03.

Example 5 rac-diisopropylamidoborane-bis-η5- (2-methyl-4-phenylinden-1-yl) zirconium η4-1,4-diphenyl-1,3-butadiene

5A) Preparation of Diisopropylaminoboro Dichloride

To a solution of trichloroborane (1.0 M, 100 ml, 0.10 mol) in methylene chloride was added dropwise, at -78°C, diisopropylamine (13.108 ml, 0.100 mol) over a 30 minute period. The solution was allowed to stir for 1 hour, during which time a white precipitate formed. The mixture was allowed to warm to room temperature and the solvent was removed under reduced pressure. The residue was dissolved in 100 ml of dry toluene, triethylamine (13.94 ml, 0.10 mol) was added and the solution was stirred overnight at room temperature. The mixture was filtered and the residue was washed with 20 ml of toluene. The solvent was removed from the combined filtrates under reduced pressure and the resulting oil was purified by vacuum distillation (25-28°C, 13 Pa, 0.11 mm), yielding 9.2 g (51 percent) of product as a colorless liquid.

1NMR (C6D6): δ 0.95 (d, 12H), 3.63 (broad multiplet, 2H).

5B) Preparation of N, N-diisopropylamino bis (2-methyl-4-phenylindenyl) borane

To 25 ml of a solution of N, N-diisopropylaminoboro dichloride (0.858 g, 4.72 mmol) in THF at room temperature was added dropwise (2-methyl-4-phenyl) lithium ionide (2.00 g, 9.44 mmol in 20 ml of THF). The mixture was stirred for 24 hours. The solvent was removed under reduced pressure. The residue was extracted with toluene (2 x 50 ml), filtered through a medium frit and the solvent was removed under reduced pressure, giving a light yellow solid (2.4 g, 97 percent).

5C) Preparation of rac-diisopropylaminoborane-bis-n5- (2-methyl-4-phenylindenyl) zirconium η4-1,4-diphenyl-1,3butadiene

N, N-diisopropylamino bis (2-methyl-4-phenylindenyl) borane (1.20 g, 2.3 mmol) was dissolved in 40 ml of toluene, 2.1 equivalents of bis (trimethylsilyl) potosic amide (0.964 g, 4.8 mmol) and the resulting mixture was stirred at room temperature for 24 hours. Volatile components were removed to

ES 2 188 235 T3 reduced pressure and the resulting orange solid was washed with 10 ml of hexane, filtered and pumped dry. The dipothetic salt residue (1.3 g, 95 percent, 2.18 mmol) was redissolved in 25 ml of toluene. (1,4-Diphenyl-1,3-butadiene) -bis (triethylphosphine) zirconium dichloride (1.318 g, 2.18 mmol) was added and the solution was stirred for 12 h at room temperature. The product mixture was filtered through diatomaceous earth filter aid and the solvent in the filtrate was removed under reduced pressure. Further purification was done by recrystallization from hexane, yielding 0.85 g (48 percent) of the desired product as a dark red solid.

1NMR (C6D6): δ 7.6 (d, 2H); 7.42-7.00 (m, 18H), 6.9 (d, 2H), 6.82 (d, 4H), 5.57 (s, 2H), 4.03 (m, 2H); 3.45-3.57 (dd, 2H), 1.8 (s, 6H); 1.28-1.33 (m, 12H).

Example 6

Diisopropylamidoboranobis- (cyclopentadienyl) zirconium dichloride preparation

6A) Diisopropylamidoboron dichloride

To a solution of BCl3 (17 g, 145 mmol) in CH2Cl2 (25 ml) at -78 ° C diisopropylamine (18.49 ml, 132 mmol) was slowly added. During the addition a white precipitate formed. The mixture was warmed to room temperature, giving a colorless solution. The solvent was removed under high vacuum at room temperature and the residue was then dissolved in benzene (45 ml). Triethylamine (18.8 ml, 134.6 mmol) was added to the solution at room temperature, the mixture was then stirred overnight at room temperature and then filtered, giving a red solution. Vacuum distillation (27-28°C, 4 Pa) gave the product (15 g, 57 percent) as a colorless liquid.

1H NMR (500MHz, CDCl3) d 1.26 (d, 12H, J = 5.8 Hz), 3.95 (br, 2H, NCH).

13C NMR (100 MHz, CDCl3) d 22.1, 49.2 (br). 1 11B NMR (115 MHz, CDC13) 29.4. MS (EI ,, m / e (intensity)): 181 (M +, 5), 166 (43), 124 (61), 43 (100).

6B) Diisopropylamidobis (cyclopentadienyl) borane

To a solution of the above product (0.39 g, 2.1 mmol) in THF (5 ml) at -78 ° C was added dropwise a solution of lithium cyclopentadienide (0.31 g, 2.1 mmol ) in THF (10 ml) at -78°C. The mixture was warmed slowly to room temperature and stirred overnight at room temperature, giving a red solution. After removal of the solvent, the residue was extracted with pentane (3x), filtered, and the pentane was then removed, giving the product (0.55 g, 100 percent) as a yellow syrup.

13B NMR (115 MHz, C6D,) d 39.8 (majority), 30.4 (minority). MS (EI, m / e (intensity)): 241 (M +, 47), 226 (40), 176 (16), 93 (100).

The GC-MS (gas chromatography-mass spectrometry) of the reaction mixture was also recorded shortly after mixing the two reagents at -78.°C, of which only cyclopentadienyldiisopropyl boron chloride was detected: MS (EI, m / e (intensity)): 211 (M +, 24), 196 (100), 154 (22).

6C) Dilithium diisopropylamidoboryldicyclopentadienide

To a solution of the above product (0.61 g, 2.53 mmol) in THF (7 ml) at -78 ° C was added lithium diisopropylamide (5.57 mmol, prepared in situ from diisopropylamine (0.780 ml , 5.57 mmol) and BuLi (2.50 M, 2.23 ml, 5.57 mmol) The mixture was warmed to room temperature and stirred for 2 hours, then the solvent was removed and the residue was washed with pentane to give the product (0.58 g, 91 percent) as a white solid.

1H NMR (360 MHz, THF-d8) d 1.24 (d, 12H, J = 6.8 Hz, NCHCH3), 4.54 (m, 2H, NCH), 5.74 (t, 4H, J = 2.4 Hz), 5.83 (t, 4H, J = 2.4 Hz).

13C NMR (100 MHz, THF-d8) d 23.9 (NCHCH3), 25.9 (NCHCH3), 49.3 (NCH), 104.4, 111.9.

11B NMR (115 MHz, THF-d8) d 44.6

IS 2 188 235 T3

6D) Diisopropylamidoboranobis (cyclopentadienyl) zirconium dichloride

To a solution of diisopropylamidobis (cyclopentadienyl) borane (0.71 g, 2.95 mmol) in Et2O (15 ml) at -78 ° C was added lithium diisopropylamide (6.93 mmol). The mixture was stirred for 2 hours at room temperature, giving a slightly cloudy solution. The solution was then added to a suspension of ZrCl4 (0.69 g, 2.95 mmol) in Et2O (15 ml) a-78°C. The resulting mixture was stirred overnight at room temperature, giving a yellowish suspension. The solvent was partially removed and the residue was concentrated and cooled to-78°C to give the product (0.50 g, 38 percent) as colorless crystals.

1H NMR (400 MHz, CDCl3) d 1.32 (d, 12H, J = 7.0 Hz), 2.92 (m, 2H), 5.65 (t, 4H, J = 2.4 Hz), 6.80 (t, 4H, J = 2.4Hz). 13C NMR (100 MHz, CDCl3) d 24.6, 49.6, 111.4, 125.7. 13B NMR (115 MHz, CDCl3) 37.6. HRMS (high resolution mass spectrum) (EI), calculated for C16H22BNC12Zr: 399.0269, found: 399.0272.

Example 7

Preparation of meso-diisopropylamidoboranobis (inden-1-yl) zirconium dichloride

7A) Diisopropylamidobis (inden-1-yl) borane

To a solution of diisopropylamidoboron dichloride (Example 3, step A) (1.10 g, 6.0 mmol) in THF (10 ml) at -78 ° C was added dropwise to a solution of lithium indenide (1 , 50 g, 12.3 mmol) in THF (40 ml) at -78°C. The mixture was warmed slowly to room temperature and stirred overnight at room temperature, giving a red solution. After removal of the solvent, the residue was extracted with CH2Cl2 (3x), filtered and the solvent was removed, giving the desired product (2.12 g, 100 percent) as a white solid:

11B NMR (115 MHz, C6D,) d 41.4. MS (EI, m / e (intensity)): 341 (M+, 8), 226 (100). HRMS (EI), calculated for C24H28BN: 341.2315, found: 341.2310.

7B) Meso-diisopropylamidoboranobis (inden-1-yl) zirconium dichloride

To a suspension of the previous product (0.39 g, 1.41 mmol) in Et2O (10 ml) at -78 ° C was added lithium diisopropylamide (prepared in situ from iPr2NH (2.62 mmol) and BuLi (2.50 M, 2.62 mmol). The mixture was stirred for one overnight at room temperature, giving an orange suspension. The solvent was removed and the residue was extracted with toluene and filtered. The toluene was then removed, giving an orange solid composed of a mixture of two stereoisomers (rac / meso, approx. 6: 4) .Repeated recrystallization (3x) from toluene at -78°C gave the pure meso isoomer (0.08 g, 14 percent) as an orange solid. Mp = 250-254°C (dec.).

1H NMR (500 MHz, CDCl3) 1.54 (d, 6H, J = 6.6 Hz), 1.57 (d, 6H, J = 6.8 Hz), 4.27 (m, 2H, NCH) , 5.91 (d, 2H, J 3.0Hz), 6.9 (m, 4H), 7.17 (t, 2H, J = 7.6Hz), 7.31 (dd, 2H, J = 8.3, 3.6 Hz), 7.53 (d, 2H, J = 8.6 Hz). 13C NMR (75 MHz, CDCl3) d 24.7, 25.0 (NCHCH3), 49.7, 100.2 (BC), 115.7, 117.2, 125.2, 125.3, 125.6 , 125.9, 126.5, 131.4. 1 11B NMR (115 MHz, CDCl3) 8 39.5. HRMS (EI), calculated for C24H26BNC12Zr: 499.0582, found, 499.0606. MS (EI, m / e (intensity)): 501 (M +, 20), 458 (7), 341 (18), 226 (93), 143 (80), 115 (99).

Example 8

Preparation of bis (dimethylamide) from rac-diisopropylamidoboranobis (inden-1-yl) zirconium

To a mixture of diisopropylamidobis (inden-1-yl) borane (Example 4, step A)) (1.01 g, 2.96 mmol) and Zr (NME2)4 (0.79 g, 0.96 mmol) was added toluene (15 ml). The resulting solution was heated to 65 ° C and stirred for 2 h, giving a bright red solution. The product consisted of two isoomers with a ratio of 6.7: 1. The solution was filtered, concentrated and cooled to-78°C, giving the pure rac isoomer (0.50 g, 33 percent) as red crystals. The structure was confirmed by X-ray diffraction analysis on individual crystals grown in toluene / hexane at -20.°CPf = 220°C (dec.).

1H NMR (500 MHz, C6D6) d 1.20 (d, 6H, J = 6.8 Hz), 1.27 (d, 6H, J = 6.6 Hz), 2.61 (s, 12H), 3.86 (in, 2H), 6.04 (d, 2H, J = 2.9 Hz), 6.74 (m, 4H), 7.00 (t, 2H, J = 7.6 Hz), 7.37 (dd, 2H, J = 8.5, 0.9 Hz), 7.52 (d, 2H, J = 8.5 Hz). 13C NMR (90 MHz, C6D6) 5 24.6, 24.9, 47.9 (NCH3), 49.6, 105.6, 112.4,

IS 2 188 235 T3

123,1, 123,2, 124,0, 124,2, 126,3, 129,1. 11B NMR (115 MHz, C6D6) d 40.8. HRMS (EI), calculated for C28H38BN3 Zr: 517.2206, found, 517.2217. MS (EI, m / e (intensity)): 517 (M +, 20), 471 (45), 429 (100), 330 (24), 226 (70).

Example 9

Rac-diisopropylamidoboranobis (inden-1-yl) zirconium dichloride

Trimethylsilyl chloride (2.0 ml, 15.76 mmol). The solution was stirred for 8 h at room temperature, giving an orange suspension. The solvent was removed and the residue was washed with pentane (2x), giving the desired product (0.40 g, 83 percent) as an orange powder. Individual crystals suitable for X-ray structural analysis were developed in mixed solvents of CH2Cl2 and hexane at -20 ° CPf = 242 ° C (dec.).

1H NMR (500 MHz, CDCl3) d 1.50 (d, 6H, J = 6.8 Hz), 1.55 (d, 6H, J = 6.6 Hz), 4.24 (heptet, 2H, J = 7.7 Hz), 5.79 (d, 2H, J = 3.0 Hz), 6.80 (dd, 2H, J = 3.2, 0.7Hz), 7.07 (t, 2H, J = 7.6 Hz), 7.28 (dd, 2H, J = 7.0, 0.7 Hz), 7.38 (t, 2H, J = 8.0 Hz), 7.58 9d, 2H , J = 8.8 Hz). 13C NMR (75 MHz, CDCl3) d 24.7, 25.0, 49.6, 98.4 (BC), 113.1, 114.1, 122.0, 123.0, 125.8, 126, 4, 127.2, 131.9. 11BRMN (115 MHz, CDCl3) d 39.2. HRMS (EI), calcd for C24H26BNCl2Zr: 499.0582, found, 499.0606. MS (EI, m / e (intensity)): 501 (M +, 20), 458 (7), 341 (18), 226 (93), 143 (80), 115 (99). Analysis calculated for C24H26BNCl2Zr: C, 57.48, H, 5.19, N, 2.79. Found: C, 57.46, H, 5.32, N, 2.68.

Example 10

Preparation of rac- (diisopropylamidoborane) bis (tetrahydroinden-1-yl) zirconium dichloride

A solution of diisopropylamidoboranobis (inden-1-yl) zirconium dichloride (Example 6) (0.16 g, 0.32 mmol) in CH2Cl2 (7 ml) was added to an autoclave reactor containing PtO2(0.0105 g) .The mixture was flushed four times with H2 (200 psi, 1.4 MPa), then H was added2 (1500 psi, 10.4 MPa) and stirred for 15 h at room temperature, giving a greenish suspension. CH2 Cl2 (25 ml) and then filtered. The solvent was removed under reduced pressure and the residue was washed with pentane (2x), giving diisopropylamidoboranobis (tetrahydro-inden-1-yl) zirconium dichloride (0.15 g, 92 percent) as a slightly greenish solid.

1H NMR (400 MHz, C6D6) d 1.06 (d, 12H, J = 6.6 Hz), 1.33 (m, 2H), 1.47 (m, 2H), 1.92 (m, 4H ), 2.05 (t, 1H, J = 4.8Hz), 2.09 (d, 1H, J = 5.0Hz), 2.34 (m, 2H), 2.53 (t, 1H, J = 5.3 Hz), 2.56 (t, 1H, J = 5.0 Hz), 3.20 (m, 2H), 3.60 (heptet, 2H, J = 6.6 Hz), 5 .01 (d, 2H, J = 2.9 Hz), 6.53 (d, 2H, J = 2.6 Hz). 13C NMR (100 MHz, C6D6) d 23.0, 23.6, 24.4, 24.7, 24.8, 27.0, 49.6, 109.7, 121.6, 124.2, 136 ,1. 11B NMR (115 MHz, C6D6) d 39.2 ppm. HRMS (EI) calculated for C24H3411BNCl2Zr 507.1208, found 507.1198.

Example 11

Preparation of ruc-N, N-diisopropylamidoborane-bis-n¡5- (2-methyl-4-naphthyl indenyl) zirconium η4-1,4-diphenyl1,3-butadiene

11A) Preparation of potassium (2-methyl-4-naphthyl) indenide

2-methyl-4-naphthylindene (1.00 g, 3.27 mmol) was dissolved in 20 ml of toluene, bis (trimethylsilyl) potassium amide (1.05 equivalents, 3.43 mmol, 0.684 g) was added reaction mixture is stirred

ES 2 188 235 T3 room temperature for 24 hours, during which time a yellow solid precipitated. Hexane (20 ml) was added and the mixture was stirred for 2 hours. The solid product was isolated by vacuum filtration through a medium porosity frit. The solid was pumped dry to give 1.10 g, 98 percent of the desired product.

IIB) Preparation of N, N-diisopropylamino bis (2-methyl-4-naphthylindenyl) borane

To a solution of N, N-diisopropylaminoboro dichloride (0.309 g, 1.70 mmol) in 25 ml of THF at room temperature was added dropwise 10 ml of a THF solution of (2-methyl-4-naphthyl ) potassium indenide (1.00 g, 3.40 mmol). The mixture was stirred for 24 hours at room temperature, the solvent was removed and the residue was extracted with toluene (2 x 25 ml). The combined extracts were filtered through a medium frit and the solvent was removed under reduced pressure to give a light yellow solid (1.0 g, 95 percent).

IIC) Preparation of rac-N, N-diisopropylaminoborane-bis-n5- (2-methyl-4-naphthyl indenyl) zirconium η4-1,4-diphenyl-1,3-butadiene

N, N-diisopropylamino bis (2-methyl-4-naphthylindenyl) borane (0.860 g, 1.38 mmol) was dissolved in 20 ml of toluene, 2.05 equivalents of bis (trimethylsilyl) potassium amide (0.566 g, 2.84 mmol) and the reaction mixture was stirred at room temperature for 24 hours. The volatile components were removed under reduced pressure and the residue was redissolved in 25 ml of toluene. While stirring at room temperature, (1,4-diphenyl-1,3-butadiene) bis (triethylphosphine) zirconium dichloride (0.835 g, 1.38 mmol) was added and the solution was stirred for 12 h at room temperature. The product mixture was filtered through diatomaceous earth filter aid and the solvent in the filtrate was removed under reduced pressure. Further purification was accomplished by recrystallization from hexane, yielding 0.27 g (21 percent) of the desired product as a dark red solid.

1H NMR (C6D6): δ 7.75-7.00 (mm, 30H), 4.82 (s, 2H), 3.85-3.95 (m, 2H); 3.62-3.70 (dd, 2H), 1.82-1.9 (dd, 2H), 1.6 (s, 6H), 1.10-1.33 (m, 12H).

Example 12 rac-1,2-bis (dimethylamidodiborane) bis (2-methyl-4-phenylinden-1-yl) zirconium n4-1,4-diphenyl-1,3-butadiene

12A) Preparation of 1,2-bis (2-methyl-4-phenylinden-1-yl) -1,2-bis (dimethylamido) -diborane

Bis (dimethylamido) diboro dichloride (0.500 g, 2.77 mmol) in diethyl ether (10 mL) was added dropwise to a solution of 2-methyl-4-phenylindene, lithium salt (1.407 g, 11.07 mmol) in dietary ether (50 ml) at 0°C. This mixture was stirred overnight at room temperature and volatiles were removed. The residue was extracted using CH2Cl2. Filtration and removal of CH2Cl2 resulted in the isolation of the desired product as a pale yellow solid (0.902 g, 62.6 percent yield). 12B) Preparation of 1,2-Bis (dimethylamido) -1,2-bis (2-methyl-4-phenylindene) diborane, dipotassium salt

1,2-bis (dimethylamido) -1,2-bis (2-methyl-4-phenylindene) diborane (0.791 g, 1.52 mmol) and KN (TMS) 2 (0.607 g, 3.04 mmol) were stirred together ) in toluene (50 ml) overnight. The reaction mixture was then refluxed for one hour, cooled to room temperature and vacuum dried. The residue was then suspended in hexane and filtered and the gold microcrystalline solid was vacuum dried (0.881 g, 97.1 percent yield).

12B) Preparation of rac- [1,2-Bis (dimethylamido) -1,2-bis (2-methyl-4-phenylindene) diborane] zirconium

ES 2 188 235 T3 (trans, trans-1,4-diphenyl-1,3-butadiene)

1,2-bis (dimethylamido) -1,2-bis (2-methyl-4-phenylindene) -diborane, dipotassium salt (0.808 g, 1.35 mmol) was slowly added as a solid to a solution of ( 1,4-diphenylbutadiene) ZrCl2 (PEt3) 2 (0.819 g, 1.35 mmol) in toluene (75 ml). This mixture was left stirring overnight. After the reaction period, the mixture will be filtered and volatiles removed, resulting in the isolation of a deep red residue. The residue was then suspended in cold hexane, filtered and dried in vacuo, resulting in isolation of the desired product as a dark red microcrystalline solid (0.501 g, 45.3 percent yield).

1NMR (C6D6): δ 1.1-1.2 (m, 2H), 2.02 (s, 6H), 2.66 (s, 6H), 2.90 (s, 6H), 3.3- 3.4 (m, 2H), 5.28 (s, 2H), 6.82 (d, 3JHH = 6.6 Hz, 2H), 6.9-7.3 (m, 14H), 7.53 (d, 3JHH = 8.4 Hz, 2H). 13C NMR (C6D6):

106.54, 119.17, 123.12, 123.39, 123.71, 124.26, 127.88, 128.51, 128.90, δ 15.10, 42.17, 44.36, 86 , 78, 93.34, 129.34, 135.76, 140.85, 145.80.

Example 13 rac-diisopropylamidoborane-bis-ri5- (2-methyl-4-phenylinden-1-yl) hafnium0

η4-1,4-difeñyl-1,3-butadiene

Hafnium tetrachloride (0.375 g, 1.17 mmol) was suspended in 40 ml of toluene. To this suspension were added triethylphosphine (0.346 ml, 2.34 mmol, via syringe), Li powder (Aldrich, low sodium content, 0.081 g, 11.7 mmol) and 1,4-diphenyl-1, 3-butadiene (0.242 g, 1.17 mmol). The reaction mixture was stirred overnight at room temperature and then filtered using a medium porosity frit and a layer of diatomaceous earth to remove unreacted Li metal. Dipotassium diisopropylamidobis (1- (2-methyl-4-phenylindenide)) borane, K2 i Pr2NB (2-Me-4-Phindenuro) 2], (0.700 g, 1.17 mmol) using 10 ml of toluene to aid transfer. The reaction mixture was stirred for 1 hour at room temperature. Toluene was removed under reduced pressure and the reaction product was extracted with hexane (twice) and filtered (medium porosity frit with diatomaceous earth layer). More product was obtained by extraction of the salt by-product using toluene and a second filtration using a medium porosity frit and a layer of diatomaceous earth.

The spectroscapic analyzes of 1H NMR indicated that the rac-iPr2The desired NB (2-Me-4-Ph-inden-1-yl) 2Hf (1,4-diphenyl-1,3-butadiene) was highly insoluble in hexane and that the unwanted meso isoomer could be removed by repeated extraction with hexane. Final isolation and purification of rac-iPr2NB (2Me-4-Ph-inden-1-yl) 2Hf (1,4-diphenyl-1,3-butadiene) is made by Soxhlet extraction using hexane. After the hexane extract turned colorless, the filter paper was removed and dried, yielding 0.042 g of rac-iPure Pr2NB (2-Me-4-Ph-inden-1-yl) 2Hf (1,4-diphenyl-1,3-butadiene) as determined by NMR spectroscopic analysis of 1 H and 13C.

1NMR (C6D6): δ 7.6 (d, 2H); 7.42-7.00 (m, 18H); 6.9 (d, 2H); 6.82 (d, 4H); 5.57 (s, 2H); 4.03, m, 2H); 3.45-3.57 (dd, 2H); 1.8 (s, 6H); 1.28-1.33 (m, 12H).

Example 14 rac-diisopropylamidoborane-bis-r5- (2-methyl-4-phenylinden-1-yl) zirconium r5 -1,4-diphenyl-1,3-butadiene

IS 2 188 235 T3

In a glove box, diisopropylamidobis (2-methyl-4-phenylinden-1-yl) borane was dissolved.

(0.125 g, 0.240 mmol) in 20 ml of dry THF and 2 equivalents of potassium bis (trimethylsilyl) amide (0.500 molar solution, 0.960 ml, 0.480 mmol) were added dropwise over a period of 10 minutes, at room temperature. , after which the solution was stirred for 4 hours. The volatile components were removed under reduced pressure and the remaining solids were redissolved in 25 ml of toluene. While stirring at room temperature, (1,4-diphenyl-1,3-butadiene) bis (triethylphosphine) zirconium dichloride (0.145 g, 0.240 mmol) was added and the resulting solution was stirred for 4 hours. The product was recovered by filtering the mixture through diatomaceous earth and removing the solvent from the filtrate under reduced pressure. Further purification was carried out by recrystallization from hexane, yielding the product as a dark red solid.

Example 15

Preparation of mc-r Pr2NC (N Pr)2) borano-bis-ni5- (2-methyl-4-phenylindenyl) zirconium η4-1,4-diphenyl-1,3butadiene

15A) Preparation of dichloride iPr2NC (Ni ) Pr) 2} boron

Diisopropylcarbodiimide (1.178 g, 9.33 mmol) was dissolved in 20 ml of toluene, cooled to 0°Cyse slowly added lithium diisopropylamide (1.00 g, 9.33 mmol) to the solution over a 5 minute period. The solution was allowed to warm to room temperature while stirring for 3 hours. Subsequently, this solution was added dropwise over a period of 30 minutes to a 1 molar solution of boron trichloride (9.33 ml, 9.33 mmol) in heptane (0°C) and allowed to warm to room temperature overnight. The solution was filtered and the solvents were removed under reduced pressure, yielding 2.3 g (97 percent) of a light yellow oil.

1NMR (C6D6): δ 3.6-3.4 (m, 2H); 3.4-3.25 (septet, 2H); 1.43 (d, 12H), 0.8 (d, 12H).

15B) Preparation of bis (2-methyl-4-phenylindenyl) (i Pr2 NC (Ni Pr) 2) borane

Dichloride dissolved i Pr2NC (Ni Pr) 2boron (0.30 g, 0.97 mmol) in 30 ml of THF and potassium (2-methyl-4-phenyl) indenide (0.476 g, 1.95 mmol) was added. The mixture was stirred for 24 hours at room temperature, followed by heating under reflux for 4 hours. The product mixture was allowed to cool to temperature and the solvent was removed under reduced pressure. The residue was extracted with toluene (2 x 50 ml), filtered through a medium frit and the solvent was removed under reduced pressure, giving a light yellow solid (0.533 g, 85 percent).

IS 2 188 235 T3

15C) Preparation of rac- (Pr2NC (Ni Pr)2) borane-bis-r]5- (2-methyl-4-naphthyl indenyl) zirconium η4-1,4-diphenyl1,3-butadiene

Bis (2-methyl-4-phenylindenyl) {i Pr2NC (Ni Pr) 2} borane (0.533 g, 0.82 mmol) in 20 ml of toluene, 2.00 equivalents of potassium bis (trimethylsilyl) amide (0.0.328 g, 1.65 mmol) were added and the reaction mixture was stirred at room temperature for 24 hours. The volatile components were removed under reduced pressure and the residue was washed with 2 x 25 ml of hexane. The volatile components were removed under reduced pressure, yielding 0.382 g (64 percent) of the solid orange dipotassium salt. A portion of this solid (0.100 g, 0.14 mmol) was dissolved in 15 ml of toluene. While stirring at room temperature (1,4-diphenyl-1,3-butadiene) bis (triethylphosphine) zirconium dichloride (0.084 g, 0.14 mmol) was added and the solution was stirred for 12 h at room temperature. The product mixture was filtered through diatomaceous earth filter aid and the solvent in the filtrate was removed under reduced pressure, yielding 0.115 g (88 percent) of crude product which existed as a rac / meso mixture. Further purification was done by recrystallization from hexanes, yielding 0.015 g (12 percent) of rac product as a dark red solid.

1H NMR (C6D6): δ 7.6-6.7 (mm, 26H); 5.55 (s, 2H); 4.05-3.90 (m, 2H); 3.5 (dd, 2H); 2.7-2.4 (m, H); 1.78 (s, 6H); 1.55 (dd, 2H); 1.25 (m, 12H); 0.95 (m, 12H).

Example 16 rac-dimethylamidoborane-bis-r¡5- (2-methyl-4-.phenylinden-1-yl) zirconium η4-1,4-diphenyl-1,3-butadiene

16A) Preparation of Dimethylamidodibromoborane

B (NMe2)3 to BBr3. The reaction was immediate and exothermic. This mixture was allowed to stir for 2 hours, after which NMR analysis showed that the reaction was essentially quantitative and complete (22.510 g, 99.9 percent yield).1NMR (C6D6): δ 2.31 (6H). 13CRMN (C6D6): δ 41.45.

16B) Preparation of Dimethylamido-bis (2-methyl-4-phenylindinyl) borane

A solution of dimethylamidodibromoborane (0.511 g, 2.38 mmol) in toluene (10 mL) was cooled to 0°C and diethyl ether (2 equivalents) was added. This mixture was then added dropwise to a solution of 2-methyl-4-phenylindene, lithium salt (1.011 g, 4.76 mmol) in THF (50 ml) at 0°C. This mixture was then allowed to stir overnight at room temperature. After the reaction period, the volatile components were removed and the residue was extracted and filtered using hexane. Removal of the hexane resulted in the isolation of a yellow oil (1.103 g, 99.9 percent yield).

16C) Preparation of dimethylamido-bis (2-methyl-4-phenylindenyl) borane, dipotassium salt

Dimethylamido-bis (2-methyl-4-phenylindenyl) borane (1.010 g, 2.17 mmol) and KN (TMS) 2 (0.866 g, 4.34 mmol) were stirred together in toluene (50 ml) overnight. The reaction mixture was then refluxed for one hour, cooled to room temperature and vacuum dried. The residue was then suspended in hexane and sefiltered and the orange microcrystalline solid was vacuum dried (1.246 g, yield> 100 percent due to residual solvent still present, as observed by NMR).

IS 2 188 235 T3

16D) Preparation of rac- [Dimethylamido-bis (2-methyl-4-phenylindene) borane] -zirconium (trans, trans-1,4-diphenyl-1,3-butadiene).

Dimethylamido-bis (2-methyl-4-pheml-indenyl) borane, dipotassium salt (1.246 g, 2.30 mmol) was slowly added as a solid to a solution of (1,4-diphenylbutadiene) ZrCl2 (PEt3) 2 (1.391 g, 2.30 mmol) in toluene (75 ml) and stirred overnight. After the reaction period, the mixture was filtered and the volatiles were removed, resulting in the isolation of a dark residue. This residue was suspended in hexane and filtered. Red crystals developed over a two hour time period from the hexane (0.222 g) filtration session. The solid on the frit was washed through the frit using toluene and a second collection of crystals developed from this mixture allowing the solution to concentrate over a period of one week by slow evaporation of toluene (0.100 g). The combination of the crystals obtained resulted in the isolation of a total of 0.322 g (18.4 percent yield) of highly pure product.

1H NMR (C6D6): δ 1.71 (s, 3H), 1.7-1.8 (m, 2H), 2.89 (s, 3H), 3.4-3.5 (m, 2H) , 5.52 (s, 2H), 6.76 (d, 3JHH = 7.2 Hz, 4H), 6.8-7.4 (m, 12H), 7.43 (d, 3JHH = 8.4 Hz, 2H). 13C NMR (C6D6): δ 15.95, 39.52, 85.43, 90.93, 104.13, 117.32, 12.49, 121.65, 122.3 (br), 123.32, 124.19, 124.32, 127.81, 127.83, 128.68, 128.74, 128.81, 136.06, 140.55, 143.86. MS (EI): m / z 759.2635 (MH)+, calculated (MH)+ 759,2610.

Example 17

Bis (trimethylsilyl) amido (r-fluoren-9-yl) (r-cyclopentadienyl) borane-zirconium dichloride. 17A) Preparation of bistrimethylsilylamido (9-fluorenyl) boron chloride

N-Butyllithium (2.5M hexane, 4.20 mL, 10.50 mmol) was added to a solution of fluorene (1.66 g, 10.00 mmol) in THF (15 mL) at -78°C. The resulting mixture was slowly warmed up and stirred at room temperature for 5 hours, giving a red solution. The solution was cooled to -78 ° C and added dropwise to a solution of bis (trimethylsilyl) amidoboron dichloride (TMS) 2NBCl2 (2.42 g, 10.00 mmol) in THF (25 ml) at -78°C, giving a light yellow solution. The solution was stirred overnight at room temperature. The volatile components were removed and the residue was extracted with pentane and filtered. The pentane was removed, giving the desired product (3.70 g, 100 percent yield) as a white solid.

1H NMR (400 MHz, CDCl3): δ 0.45 (s, 18H), 4.41 (s, 1H), 7.34 (dt, 2H, J = 7.4, 1.1 Hz), 7, 42 (t, 2H, J = 7.3 Hz), 7.49 (d, 2H, J = 7.6 Hz), 7.87 (d, 2H, J = 7.4 Hz). 13C NMR (100 MHz, CDCl3) δ 4.6, 121.0, 125.4, 127.2, 127.3, 143.0, 145.9. 1 11B NMR (115.5 MHz, CDCl3) δ 46.6.

17B) Preparation of bis (trimethylsilyl) amido (9-fluorenyl) (cyclopentadienyl) borane

A solution of CpNa / THF (0.24 g, 2.40 mmol) in THF (15 ml) at -78 ° C was added dropwise to a solution of bistrimethylsilylamido (9-fluorenyl) boron chloride (0.89 g, 2.40 mmol) in THF (15 ml) at -78°C. The resulting yellow solution was slowly warmed to room temperature with stirring and stirred overnight. The volatiles were removed under reduced pressure and the residue was extracted with pentane and filtered. The pentane solution was concentrated and cooled to -78°C to give the desired product (0.57 g, 59 percent) as a white solid.

1H NMR (400 MHz, C6D6): δ 0.20 (s, 18H), 1.71 (t, 2H, J = 1.4 Hz), 4.33 (s, 1H), 5.93 (m, 1H), 6.13 (m, 1H), 6.69 (dd, 1H, J = 14, 1.5 Hz), 7.09 (dt, 2H, J = 7.2, 1.5 Hz), 7.19 (dt, 2H, J = 7.4, 1.7 Hz), 7.46 (dd, 2H, J = 7.4, 1.1 Hz), 7.70 (dd, 2H, J = 7.6, 0.8 Hz). 13C NMR (100 MHz, C6D6) δ 5.1, 43.4, 120.6, 125.8, 126.7, 127.2, 132.2, 139.5, 142.9, 143.1, 147 ,4. 11B NMR (115.5 MHz, C6D6) δ 51.6. HRMS (EI) calculated for C23H29BNSi, (M-CH3), 386.1932; found, 386.1945.

17C) Bis (trimethylsilyl) amidoborane (r-cyclopentadienyl) (r-fluoren-9-yl) zirconium dichloride

A solution of lithium diisopropylamide (prepared in situ from iPr2NH (0.54 ml, 3.84 mmol) and BuLi (2.5 M hexane, 1.61 mil, 4.03 mmol)) in THF (10 ml ) was added to a solution of bis (trimethylsilyl) amido (9-fluorenyl) (cyclopentadienyl) borane (0.77 g, 1.92 mmol) in THF (10 mL) at -78°C. The resulting mixture was allowed to warm to room temperature and stirred overnight, giving a dark red solution. The volatile components were removed, giving an orange solid which was then dissolved in toluene (15 ml). The toluene solution was added to a suspension of ZrCl4 (0.40 g, 1.9 mmol) in toluene (8 ml) at -78°C. The mixture was warmed to room temperature and stirred for one

ES 2 188 235 T3 night, giving a dark red suspension. The volatile components were removed under reduced pressure and the residue was extracted with toluene and then filtered. The volatile components were removed under reduced pressure and the residue was washed with pentane (3x), giving the product as a red solid.

mp = 252-254 (dec.). 1H NMR (400 MHz, CDCl3): δ 0.26 (s, 9H), 0.50 (s, 9H), 5.44 (t, 2H, J = 2.4 Hz), 6.45 (t, 2H, J = 2.4 Hz), 7.19 (d, 2H, J = 8.4 Hz), 7.31 (t, 2H, J = 7.5 Hz), 7.62 (t, 2H, J = 7.8 Hz), 8.12 (d, 2H, J = 8.4 Hz). 13C NMR (75 MHz, CDCl3) δ 4.8, 5.9, 105.3, 121.4, 122.9, 124.4, 125.4, 125.7,

129,1, 143,0. 11B NMR (115.5 MHz, CDCl3) δ 48.2. HRMS (EI) calculated for C24H30BNSi2Cl2Zr: 559.0434; found, 559.0443.

Example 18

Diisopropylamidoborane (r¡-cyclopentadienyl) (r¡-fluoren-9-yl) zirconium dichloride.

18A) Preparation of diisopropylamido (9-fluorenyl) boron chloride

The reaction conditions of Example 17A) were substantially repeated with the exception that diisopropylamidodichloroboro was used instead of bis (trimethylsilyl) amido-dichloroboro. At the end of the reaction, the solvent was removed, the residue was extracted with CH2Cl2 and filtered. The volatile components were removed, giving the product (0.91 g, 98 percent) as a yellowish solid.

1H NMR (400 MHz, CDCl3): δ 1.36 (a, 6H), 1.79 (a, 6H), 4.41 (a, 1H), 7.35 (t, 2H, J = 7.7 Hz), 7.42 (t, 2H, J = 7.5 Hz), 7.50 (a, d, 2H, J = 4.7 Hz), 7.88 (d, 2H, J = 7.3 Hz). 13C NMR (100 MHz, CDCl3) δ 24.5 (a), 43.2 (a), 48.5 (a), 120.2, 124.4, 126.4, 126.9, 141.1 ( a), 146.9. 11B NMR (115.5 MHz, CDC13) δ 37.2. HRMS (EI) Calculated for C19H23BNCl, 311.1612; found, 311.1613.

18B) Diisopropylamido (cyclopentadienyl) (9-fluorenyl) borane

The reaction conditions of Example 17B were substantially repeated with the exception that diisopropylamido (9-fluorenyl) boron was used in place of bis (trimethylsilyl) amido (9-fluorenyl) boron chloride. The reaction of CpNa / THF (0.96 g, 9.60 mmol) and diisopropylamido (9-fluorenyl) boron chloride (2.98 g, 10.00 mmol) gave a reaction mixture which was extracted with hexane and leaked. The volatiles were removed, giving the product (2.11 g, 62 percent) as a yellow solid.

HRMS (EI), calculated for C24H28BN, 341, 2315, found, 341.2329.

18C) Preparation of diisopropylamidoborane (r¡-cyclopentadienyl) (r¡-fluoren-9-yl) zirconium dichloride

The reaction conditions of Example 17C) were substantially repeated with the exception that diisopropylamido (9-fluorenyl) boron (1.39 g, 4.08 mmol) was used instead of bis (trimethylsilyl) amido (9-fluorenyl) boron. The crude reaction mixture from this reaction was extracted with toluene and filtered. The solution was concentrated, pentane was added and cooled to -78 ° C, giving the product (0.75 g, 36 percent yield) as a red solid.

Mp = 280-282°C. 1H NMR (500 MHz, C6D6): δ 1.01 (d, 6H, J = 6.6 Hz), 1.22 (d, 6H, J = 6.9 Hz), 3.67 (pent., 1H , J = 6.6 Hz), 3.80 (pent., 1H, J = 6.6 Hz), 5.30 (t, 2H, J = 2.4 Hz), 6.38 (t, 2H, J = 2.4 Hz), 7.05 (d, 2H, J = 8.1 Hz), 7.12 (t, 2H, J = 7.5 Hz), 7.46 (t, 2H, J = 7.5 Hz), 7.92 (d, 2H, J = 8.5 Hz). 13C NNIR (90 MHz, CDC13) δ 24.2, 25.4, 49.1, 49.8, 106.9, 122.2, 123.2, 125.4, 125.8, 129.0, 147 , 9,

157,1. 11B NMR (115.5 MHz, C6D6) δ 39.4. EA (elemental analysis), calculated for C24H28BNZrCl2: C, 57.25, H, 5.57, N, 2.78. Found: C, 55.44; H, 5.30; N, 2.62.

Example 19 bis (dimethylamide) of bis (trimethylsilyl) amidoborane bis (r-inden-1-yl) zirconium

Bis (trimethylsilyl) amidoborobis (inden-1-yl) was prepared by the reaction of lithium indenide (0.50 g, 4.10 mmol) and bis (trimethylsilyl) amidoboron dichloride (0.48 g, 2.00 mmol) in THF to give the product (0.75 g, 94 percent) as a yellowish solid.

1H NMR (400 MHz, C6D6, major isomer): δ 0.32 (s, 18H), 3.64 (s, 2H), 6.08 (dd, 2H, J = 5.5,

1.8 Hz), 6.48 (dd, 2H, J = 5.2 Hz), 6.82 (d, 2H, J = 7.3 Hz), 0.93 (dt, 2H, J = 7, 1, 1.2 Hz), 7.20 (m, 4H).

IS 2 188 235 T3 11B NMR (115.5 MHz, C6D6) δ 56.8. HRMS (EI) calculated for C24H32BNSi2, 401.2166; found, 401.2182. AE, Calculated for C24H32BNSi2, C, 71.82; H, 7.98; N, 3.49. Found: C, 70.06; H, 8.06; N, 3.36.

Bis (trimethylsilyl) amidoboro bis (inden-1-yl) (0.27 g, 0.67 mmol) and Zr (NMe2) 4 (0.18 g, 0.67 mmol) were then combined in toluene (10 ml) for 2 hours at 65 ° C, giving a red solution. The volatile components were removed under reduced pressure, yielding the product as a red foam.

1H NMR (400 MHz, C6D6): δ 0.26 (s, 18H), 2.53 (s, 12H), 5.95 (d, 2H, J = 2.9 Hz), 6.64 (d, 2H, J = 2.9 Hz), 6.68 (t, 2H, J = 7.5 Hz), 6.95 (t, 2H, J = 7.6 Hz), 7.30 (d, 2H, J = 8.5 Hz), 7.45 (d, 2H, J = 8.8 Hz). 13C NMR (100 MHz, C6D6) δ 5.6, 47.9, 105.1, 111.5, 122.2, 122.9, 124.2, 126.4, 128.5. 11B NMR (115.5 MHz, C6D6) δ 50.3. HRMS (EI) calculated for C28H42BN3Si2Zr, 577.2057; found, 577.2061.

Example 20

Bis (trimethyl) silylamidobis (n¡-inden-1-yl) boranozirconium dichloride

Bis (trimethylsilyl) amidoboron bis (inden-1-yl) (0.45 g, 1.12 mmol) and Zr (NMe2) 4 (0.30 g, 1.12 mmol) were combined in THF, giving an intermediate that it was not further purified. The volatiles were removed under reduced pressure and replaced with CH2Cl2 (10 mL). The mixture was stirred with trimethylsilane chloride (1.42 mL, 11.20 mmol) overnight at room temperature. The volatile components were removed again under reduced pressure and the residue was extracted with CH2Cl2 and filtered. The solution was concentrated, layered with pentane, and cooled to -78 ° C to give the desired product (0.54 g, 86 percent) as an orange solid.

1H NMR (500 MHz, C6D6): δ 0.20 (s, 18H), 5.54 (d, 2H, J = 3.3 Hz), 6.68 (dd, 2H, J = 2.1, 0 , 9 Hz), 6.85 (t, 2H, J = 7.0 Hz), 7.04 (dd, 2H, J = 8.1, 1.1 Hz), 7.17 (m, 2H, overlapped with the peak of the solvent residue), 7.33 (d, 2H, J = 8.4 Hz). 13C NMR (100 MHz, C6D6) δ 5.3, 112.8, 113.0, 123.6, 126.5,

127,1, 127,8, 132,1. 11B NMR (115.5 MHz, C6D6) δ 48.5. HRMS (EI) calculated for C24H30BNSi2Cl2Zr, 559.0434; found, 559.0432.

Example 21

Preparation of rac-diisopropylamidoborane-bis-n¡5- (2-isopropyl-4-phenyl indenyl) zirconium n¡4-1,4-diphenyl-1,3butadiene

21A) 2-Isopropyl-4-phenyl indene

Sodium hydride (2.1 g, 60 percent dispersion in oil) was placed in a 500 ml flask under a nitrogen atmosphere. Hexane (approximately 20 ml) was added to remove the oil and the mixture was stirred for a short time. After stopping the stirring, the NaH was allowed to settle and the liquids were withdrawn using a syringe. This procedure was repeated one more time, then THF (200 ml) was added to the NaH and the suspension was cooled with an ice bath. Diethyl isopropylmalonate (10.10 g, 50.00 mmol) in THF (100 ml) is added via an addition funnel over 30 minutes. After the addition of the malonate is complete, the solution is stirred for an additional 40 minutes. A solution (30 ml) of 2-phenylbenzyl bromide (12.5 g, 50.5 mmol) in THF was added via an addition funnel and the mixture was stirred overnight. The following morning 100 ml of 1 N amoemic chloride were added. The solution was diluted with ether (200 ml) and the organic layer was washed with brine, dried over Na2SO4 and distilled from the solvent under reduced pressure. The orange-red oil was used without further purification.

IS 2 188 235 T3

The crude alkylation product was dissolved in ethanol (300 ml) and water (75 ml). Potassium hydroxide (20 g) was added and the mixture heated under reflux overnight. After cooling, the ethanol was distilled under reduced pressure. Hexane was added and stirred for 1 hour to dissolve any unwanted organics. The hexane was decanted and water (approximately 150 ml) was added. The solution was acidified (to pH 1) by the addition of concentrated HCl. The desired carboxylic product was extracted with ether, dried over Na2SO4, and distilled under reduced pressure. The NMR spectrum of the crude product (10.74 g, 80 percent) indicated that the hydrolysis of the ester and the decarboxylation were complete. The crude product, which solidified to a chestnut solid, was used without further purification.

Thionyl chloride (50 ml) was added to the carboxylic acid and the mixture was stirred overnight at room temperature to dissolve the acid. The excess thionyl chloride was removed under reduced pressure and the remaining acid chloride was dissolved in methylene chloride (75 ml). This solution was added dropwise via an addition funnel to a suspension of aluminum chloride (5.70 g, 42.5 mmol) in methylene chloride (25 ml) and cooled with an ice bath. The reaction was allowed to slowly warm to room temperature and stirred overnight. The solution was poured onto ice (approximately 100 ml) and vigorously stirred for 1 hour. The orgaonic layer was separated, the aqueous layer was washed once with ether, and the combined organic layers were washed with brine, dried over Na2SO4, and distilled under reduced pressure. The crude 2-isopropyl-4-phenylindanone (10.0 g) as an orange-brown oil was used without further purification.

2-Isopropyl-4-phenylindanone (12.1, 48 mmol) was stirred in a mixture of THF and methanol (100 ml; 2/1) while adding sodium borohydride (1.5 g, 40 mmol). After stirring overnight, ice (approximately 50 ml) was added and the mixture was stirred for 0.5 h. THF and MeOH were removed under reduced pressure. Ether (approximately 250 ml) was added, the pH was adjusted to pH 1 by the addition of aqueous HCl, and the ether layer was separated. The ether was washed with a saturated sodium bicarbonate solution and then with brine, dried over Na2SO4 and evaporated under reduced pressure. The mixture of alcohol isomers (11.0 g, 43.5 mmol, 90 percent) was obtained as a coppery brownish solid. It was used without further purification.

The crude mixture of isomeric alcohols was dissolved in toluene (150 ml), to which p-toluene sulfoonic acid (0.5 g) was added. The solution was refluxed in a flask equipped with a Dean-Stark trap for 1.5 h and then cooled. Solid sodium bicarbonate was added and the mixture was stored overnight in a refrigerator. The following morning water (100 ml) was added and the organo layer was separated, dried over Na2SO4 and distilled under reduced pressure. The product, 2-isopropyl-4-phenylindene (10.4 g), was obtained as a brown oil. GC analysis indicated> 96 percent air purity. This material was stored cold in an inert atmosphere until ready for further conversion.

1H-NMR (CDCl3): δ 1.18 (d, 6H), 2.74 (sept, 1H), 3.39 (s, 2H), 6.53 (s, 1H), 7.09-7, 55 (m, 8H).

21B) Lithium 2-Isopropyl-4-phenylindenide

To a solution (25 ml) of 2-isopropyl-4-phenylindene (3.34 g, 14.25 mmol) in toluene, in an argoon-filled glove box was added n-butyl lithium (5,500 ml, 13.75 mmol). The mixture was stirred at room temperature overnight. Toluene was removed under reduced pressure. Hexane (20 ml) was added and removed under reduced pressure and then added again (50 ml). The mixture was stirred for 1 h and then filtered, washed with approximately 15 ml of hexane and the filtrate was dried in vacuo. The lithium indenide product (3.09 g) was obtained as an orange-brown powder. This material was stored in a glove box until needed.

1H-NMR (d8-THF): δ 1.27 (d, 6H), 3.02 (sept, 1H), 5.84 (s, 1H), 6.06 (s, 1H), 6.42- 6.51 (m, 2H), 7.15 (t, 1H), 7.18 (d, 1H), 7.26 (t, 2H), 7.82 (d, 2H). 13C-NMR (d8-THF): ppm147.00,141.54,130,59,130.40, 129.20, 128.16, 126.70, 125.02, 118.68, 113.92, 113.40, 91.01 , 89.77, 30.62, 25.78.

21C) N, N-diisopropylamido bis (2-isopropyl-4-phenylindenyl) borane

To 25 ml of a toluene solution of N, N-diisopropylamidoboron dichloride (0.501 g, 2.75 mmol) at room temperature was added dropwise (2-isopropyl-4-phenyl) potassium indenide (1.50 g , 5.51 mmol in 20 ml of toluene). The mixture was heated to reflux and stirred for 6 hours. The solution was cooled to room temperature, filtered through a medium frit, and the solvent was removed under reduced pressure to give a light yellow solid (1.57 g, 99 percent). This material was further purified by column chromatography (silica gel / hexane), yielding 0.6 g (38 percent) of a yellow solid.

ES 2 188 235 T3 clear (96 percent purity by GC).

21D) rac-diisopropylamidoborane-bis-n5- (2-isopropyl-4-phenyl indenyl) zirconium η4-1,4-diphenyl-1,3-butadiene

In a glove box, N, N-diisopropylamino bis (2-isopropyl-4-phenylindenyl) borane (0.380 g, 0.660 mmol) was dissolved in 20 ml of toluene, 2.1 equivalents of bis (trimethylsilyl) potassium amide were added. (0.276 g, 1.38 mmol) and the resulting mixture was stirred at room temperature for 24 hours. The volatiles were removed under reduced pressure and washed. The resulting orange solid was combined with 10 ml of hexane, filtered and pumped dry. The dipotassium salt residue (0.415 g, 97 percent, 0.635 mmol) was redissolved in 20 ml of toluene and (1,4-diphenyl-1,3-butadiene) bis (triethylphosphine) zirconium dichloride (0.384 g, 0.635 mmol) was added. ). The solution was stirred for 2 h at room temperature, followed by heating to 80°C for 6 hours. The product mixture was cooled to room temperature, filtered through diatomaceous earth and the solvent in the filtrate was removed under reduced pressure. Further purification was done by recrystallization from hexane, yielding 0.21 g (36 percent) of product as a dark red solid.

1H NMR (C6D6): δ 7.62 (d, 2H), 7.42-6.7 (mm, 24H); 5.79 (s, 2H), 4.5, sept., 2H), 3.45-3.57 (dd, 2H); 2.8-2.9 (sept., 2H), 1.65-1.72 (dd, 2H), 1.35 (d, 12H), 1.2-1.3 (m, 12H).

Example 22 rac-Diisopropylamidoborane-bis-n5- (2-methyl-4-phenylinden-1-yl) zirconium n4-1,4-diphenyl-1,3-butadiene supported

A toluene solution of methyldi (octyl) ammonium hydroxyphenyltris- (pentafluorophenyl) borate (825 μ !, 0.040 M, 33.0 μmol, obtaining the ammonium cation from a mixture of commercially available amines such as methylbis-tallowamine) and A solution in triethyl aluminum toluene (TEA) (363 µ! 0.10 M, 36.3 µmol) were combined and mixed for 30 seconds. The resulting solution was then added to 1.0 g of TEA-treated solid (Grace-Davison 948 solid, calcined at 250 ° C for 4 h, treated with 1.5 mmol TEA / g, washed with toluene and mixed hexanes and dried at reduced pressure). The mixture was shaken by hand to break up the lumps and then mechanically shaken for 5 minutes. The volatile components were then removed under reduced pressure. A toluene solution of rac-diisopropylamidoborane-bis-n was added5- (2-methyl-4-phenylinden-1-yl) zirconion4-1,4-diphenyl-1,3-butadiene (1500 µl 0.020 M, 30.0 µmol). The mixture was shaken by hand to break up the lumps and then mechanically shaken for 5 minutes. The volatile components were removed one more time under reduced pressure, giving the supported catalyst as a blue / gray solid.

Example 23 rac-Dimethylamidoborane-bis-n5- (2-methyl-4-phenylinden-1-yl) zirconium n4 -1,4-diphenyl-1,3-butadiene supported

A toluene solution of hydroxyphenyltris (pentafluorophenyl) methyldi (octyl) ammonium borate (578 μ! 0.040 M, 23.1 μmol) and a toluene solution of triethyl aluminum (254 μ! 0.100 M, 25.4 μmol) were added and mixed for 30 seconds. This solution was then added to 0.70 g of TEA-treated silica (Grace-Davison 948 silica, calcined at 250 ° C for 4 h, treated with 1.5 mmol TEA / g, washed with toluene and hexanes and dried at reduced pressure). The mixture was shaken by hand to break up the lumps and then stirred mechanically for 5 minutes. The volatile components were then removed under reduced pressure. A toluene solution of rac-dimethylaminoboranobis-n was added5- (2-methyl-4-phenylinden-1-yl) zirconium n4-1,4-diphenyl-1,3-butadiene (1050 µl 0.020 M, 21.0 µmol). The mixture was shaken by hand to break up lumps and then mechanically shaken for 5 minutes. The volatile components were then removed under reduced pressure, giving a solid dark greenish blue.

Example 24 rac-Diisopropylamidoborane-bis-n5- (2-methyl-4-phenylinden-1-yl) zirconium n4-1,4-diphenyl-1,3-butadiene supported

A toluene solution of methylbis (octadecyl) ammonium bis (tris (pentafluorophenyl) alumininane) imidazolide (689 μ! 0.0479 M, 33.0 μmol, prepared according to USSN 09 / 251,664, filed February 17, 1999) was added to 1.0 g of ... treated with TEA (Grace-Davison 948 solid, calcined at 250°C for 4 h, treated with 1.5 mmol TEA / g, washed with toluene and hexanes and pressure dried

ES 2 188 235 T3 reduced). The mixture was shaken manually to break up the lumps and then stirred mechanically for 5 minutes. The volatile components were then removed under reduced pressure. A toluene solution of rac-diisopropylamidoborane-bis-r was added5- (2-methyl-4-phenylinden-1-yl) zirconium r4-1,4-diphenyl1,3-butadiene (1500 gl, 0.020 M, 30.0 gmol). The mixture was shaken by hand to break up the lumps and then mechanically shaken for 5 minutes. The volatile components were then removed under reduced pressure, giving a blue solid.

Example 25 rac-Dimethylamidoborane-bis-η5- (2-methyl-4-phenylinden-1-yl) zirconium r¡4-1,4-diphenyl-1,3-butadiene supported

In an argon atmosphere, a toluene solution of methylbis (octadecyl) ammonium bis (tris (pentafluorophenyl) alumina) imidazolide (689 gl, 0.0479 M, 33.0 gmol) was added to 1.0 of ... treated with TEA (Grace-Davison 948 solid, calcined at 250°C for 4 h, treated with 1.5 mmol TEA / g, washed with toluene and hexanes and dried under reduced pressure). The mixture was shaken by hand to break up the lumps and then mechanically shaken for 5 minutes. The volatile components were then removed under reduced pressure. A toluene solution of rac-dimethylamidoborane-bis-r was added5- (2-methyl-4-phenylinden-1-yl) zirconium r4-1,4-diphenyl-1,3-butadiene (1500 gl, 0.020 M, 30.0 gmol). The mixture was shaken by hand to break up the lumps and then stirred mechanically for 5 minutes. The volatile components were then removed under reduced pressure, giving a light blue solid.

Polymerization in the gas phase

In a stirred 2.5 L fixed bed autoclave, 200 g of dry NaCl containing 0.1 g of KH was introduced as scavenger. Agitation was started at 300 rpm. The reactor was pressurized to 0.8 MPa of ethylene and heated to 72°C. 1-Hexene was introduced into the reactor followed by the addition of hydrogen. In a separate container, 0.05 g of catalyst was mixed with 0.1 g or more of KH as a scavenger. The combined catalyst and scavenger were subsequently injected into the reactor. Ethylene pressure was maintained as needed while hexene and hydrogen were supplied to the reactor to maintain their respective concentrations. The temperature of the reactor was regulated by means of a circulating water bath. After 90 minutes, the reactor was depressurized and the salt and polymer were removed. The polymer was washed with copious amounts of distilled water to remove the salt, dried at 60°C and then stabilized by adding a hindered phenol antioxidant (IrganoxTM 1010 from Ciba Geigy Corporation) and 133 mg of a phosphorus stabilizer. Activity values were calculated based on ethylene uptake. The results are indicated in Table 1

TABLE 1

<td>Process</td><td>Cat.</td><td>hexene (ppm)</td><td>H2 (ppm)</td><td>Activity1</td><td>Density1 2</td><td>MMI3 4(dg / m)</td><td>Mw x 10-3</td><td>MWD</td><td>I10 / I2</td>

1 g of polymer / g of cat. + cocat./h/(MPa x 0.1)2 density is determined by a displacement technique using methyl ethyl ketone 3 Fusion onyx, I2, ASTM D-1238, 190°C / 2.16 kg, I10 ASTM D-1238, 190°C / 10 kg 4 reaction carried out for 5 hours

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10351198	United States of America	P	1998-10-08
10351198	United States of America	P	1998-10-08
19980103511P	United States of America	–	1998-10-08
19990383995	United States of America	–	1999-08-26
38399599	United States of America	A	1999-08-26
38399599	United States of America	A	1999-08-26
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383995	–	–	–
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US19990383995	–	–	–

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Bridged metal complexes for gas phase polymerizations

Abstract

Term

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DESCRIPTION

IS 2 188 235 T3

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TABLE 1

Priority claims10

Members69

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