Indian Patents
Title of Invention

AN OLEFIN POLYMERIZATION PROCESS
Abstract AN OLEFIN POLYMERIZATION PROCESS
Full Text FORM 2
THE PATENTS ACT, 1970
[39 OF 1970]
&
THE PATENTS RULES, 2003
COMPLETE SPECIFICATION
[See Section 10; rule 13]
"AN OLEFIN POLYMERIZATION PROCESS"
BP CHEMICALS LIMITED, a British company of Britannic House, 1 Finsbury Circus, London EC2M 7BA, United Kingdom,
The following specification particularly describes the nature of the invention and the manner in which it is to be performed:-

The present invention relates to an olefin polymerization process.
This invention relates to the use of certain bridged Group 4 transition metat complexes possessing a unique bridging structure in a gas-phase olefin polymerization catalyst. The unique bridge consists of either boron or aluminum atoms which are further ligated with nitrogen containing groups. The unique bridging structures in the complexes provides for gas-phase olefin polymerization catalysts with exceptionally high catalytic efficiency, and processes giving unique polymer properties.
In Anqew. Chem. Int. Ed. Engl., 36, 21, p2338-2340 (1997) and in Phosphorus. Sulfur, and Silicon. 124 & 125, p561-565 (1997) amido substituted boron bridged ferrocenophanes useful for forming poly(ferrocenes) by a ring opening polymerization were disclosed. The synthesis and characterization of Group 1 and 2 metal and tin complexes of 1,2-bis(dimethylamino)-1,2-di-9-fluorenyfdiboranes were disclosed in Chem. Ber.. 127, p1901-1908. (1994). Diboranes having structure similar to those employed in the foregoing study were disclosed by the same researchers in Eur. J. Inorq. Chem.. p505-509 (1998). Ferrocenophane derivatives of similar bisboranes for further molecular property studies were disclosed by J. Orqanomet. Chem.. 530 p117-120.(1997). In Qroanometallics. 16, p4546-4550 (1997) boron bridged ansa metallocene complexes including dimethylsulfide and phosphine adducts thereof of possible use in Ziegler-Natta-type olefin polymerizations were disclosed.
In the patent literature, bridged metal complexes for use as olefin polymerization catalyst components, including such complexes containing one or more boron atoms in the bridge are generically disclosed by EP-A-416,815 and WO 98/39369.
The present invention relates to the use of certain bridged Group 4 transition metal complexes as olefin polymerization catalysts in a gas-phase olefin polymerization, wherein said complexes correspond to the following formulas:

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

Y1 and Y2 are independently an anionic, cyclic or non-cyclic, re-bonded group, NR1".PR1NR1"or PFlV,
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 each occurrence is:

Rr is independently each occurrence hydrogen, a hydrocarbyl group, a tri(hydrocarbyl)silyl group, or a tri(hydrocarbyl)silylhydrocarbyl group, said R1 groups containing up to 20 atoms not counting hydrogen;
R5 is R1 or N(R1)"k; and
two R1 groups together or one or more R" groups together with R5 may optionally be joined to form a ring structure.
It is understood that the foregoing metal complexes may exist as dimers and that one or more Lewis bases may optionally be coordinated with the complex or the dimer thereof and that when Y1 or Y2 are the neutral ligands, NR"2 or PRV the bond to M is a coordinate-covalent bond rather than a covalent bond. In addition, when T is R"2N 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 accurately depicted by the formula R"12N=B. In addition, suitable catalyst compositions desirably additionally comprise an activating cocatalyst and a support.

Formula 1A or Formula 2A wherein Z, T, R1 and R5 are as defined above;
The foregoing metal complexes are produced by reaction of a metallated derivative of a compound of one of the formulas:

Y1 and Y2 are an anionic, cyclic or non-cyclic, re-bonded group, NR", or PR1; and
R4 is hydrogen or a trimethylsilyl group,
with a metal salt of the formula MY34, where M is a Group 4 metal, and Y3 is a leaving group, especially halide. The reactants may be combined either as neat reagents or in an inert solvent. Temperatures from -100 9C to 150 9C are preferred.
In a particularly preferred embodiment, the complexes of formula 1 and formula 2 are prepared in high racemic purity in the +2 formal oxidation state by contacting the metallated derivatives of compounds of formula 1A or formula 2A, with a Group 4 precursor of the formula 3:

Formula 3
wherein M and Y3 are defined as above,
R6 independently each occurrence is hydrogen, a hydrocarbyl group, a tri(hydrocarbyl)silyl group, or a tri(hydrocarbyl)silylhydrocarbyl group, said R6 groups containing up to 20 atoms not counting hydrogen; and
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 hydrocarbon or ether, employing temperatures from -100 oC to 150 o-C. This technique is similar to that disclosed in United States patent application 265,641, filed March 10,1999, differing in that different starting reagents are employed.
The process of the present invention can be used in combination with one or more additional polymerization processes either in parallel or series, using the same or different reactors.
Because the catalyst compositions possess improved catalytic efficiencies and improved thermal stability, they are particularly adapted for use under higher operating temperatures and poor thermal transport conditions, such as are commonly encountered under gas phase polymerization conditions.
All references to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 1997. Also, any references to a Group or Groups shall be to the Groups or Groups reflected

in this Periodic Table of the Elements using the IUPAC system for numbering groups. By the term "-bonded" as used herein is meant that bonding occurs through an interaction involving delocalized electrons. Finally, by the term, "leaving group" is meant a ligand that is readily displaced by another ligand under ligand exchange conditions.
The present Group 4 transition metal complexes contain a unique bridging group: (T-Z) or (T-Z)2. which imparts improved catalytic properties when used in combination with one or more activating cocatalysts or activating techniques in the presence of addition polymerizable monomers. While not desiring to be bound by theory, it is believed that the improvement in catalytic properties for such complexes may be due to electron donating or electron withdrawing properties of the Y1 and Y2 moieties.
Preferred Gjgup_4_transjtLon metal complexes are those that correspond to formula 1 or 2 are represented in formulas 4, 5, 6, 7, 8 and 9:

wherein M, Z, T, Q and j are as defined above;
R2 is hydrogen, or a hydrocarbyl, halohydrocarbyl, dihydrocarbylamino-hydrocarbyl, tri(hydrocarbylsilyl)hydrocarbyl, Si(R3)3, N(R3)2, or OR3 group of up to 20 carbon or silicon atoms, and optionally two adjacent R2 groups can be joined together, thereby forming a fused ring structure, especially an indenyl ligand or a substituted indenyl ligand; and

R3 is independently hydrogen, a hydorcarbyl group, a trihydrocarbylsilyl group or a trihydrocarbylsilylhydorcarbyl group, said R3 having up to 20 atoms not counting hydrogen.
When M is in the +4 oxidation state, j = 2 and Q independently each occurrence is halide, hydride, hydrocarbyl, silylhydrocarbyl, hydrocarbyloxide, dihydrocarbylamide, said Q having up to 20 atoms not counting hydrogen. Alternatively, two Q groups may be joined together to form an alkanediyl group or a conjugated C4-10 diene ligand which is coordinated to M in a metallocyclopentene fashion.
When M is in the +3 oxidation state, j = 1 and Q is either 1) a monovalent anionic stabilizing ligand selected from the group consisting of alkyl, cycloalkyl, aryl, silyl, amido, phosphido, alkoxy, aryloxy, sulfido groups, and mixtures thereof, and being further substituted with an amine, phosphine, ether, or thioether containing substituent able to form a coordinate-covalent bond or chelating bond with M said ligand having up to 50 atoms not counting hydrogen; or 2) a C3.10 hydrocarbyl group comprising an ethylenic unsaturation able to form an T|3 bond 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 -complex with M.
Specific examples of the above metal complexes wherein M is in the +4 oxidation state are shown below in formulas 4a-9a, wherein the definitions of M, Z, R1, R2, and R3 are as defined above:
Specific examples of the above metal complexes wherein M is in the +4 oxidation state are shown below in formulas 4a-9a, wherein the definitions of M, Z, R1, R2, and R3 are as defined above:


unsaturation able to form an n3 bond with M. Most highly preferred examples of such Q ligands are 2-N.N-dimethylaminobenzyl, allyl, and 1-methyl-allyl.
Specific examples of the above metal complexes wherein M is in the +2 oxidation state are shown below in formulas 4c-9c, wherein the definitions of M, Z, R
R2, and R3 are as defined above:

wherein Q, each occurrence is a neutral conjugated diene, optionally substituted with one or more tri(hydrocarbyl)silyl groups or tri(hydrocarbyl)silylhydrocarbyl groups, said Q having up to 30 atoms not counting hydrogen and forming a -complex with M. Most highly 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 foregoing formulas, R1" independently each occurrence is C1-4 alkyl or phenyl, more preferably methyl or isopropyl, most preferably methyl, Y1 and Y2 are both inden-1-yl, 2-alkyl-4-arylinden-1-yl, or 3-alkylinden-1-yl, or Y" is cyclopentadienyl or alkyl-substituted cyclopentadienyl 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 R" is methyl or isopropyl, most preferably methyl. During synthesis of these complexes, the use of methyl R" groups gives elevated, often quantitive, yields of the rac isomer.

In formulas 5a-c, 6a-c, 8a-c and 9a-c, M is even more preferably titanium, 2 is boron and R" is C1-4 alkyl or phenyl, most preferably methyl or isopropyl.
Most highly preferred metal complexes are those of formulas 4a-c and 8a-c wherein Y"1 and Y2 are both inden-1-yl, 2-methyl-4-phenylinden-1-yl, 3-isopropylinden-1-yl, or 3-t-butyiinden-1-yl groups, especially compositions comprising greater than 90 percent rac isomer.
Specific, but not limiting, metal complexes included with the invention described in the foregoing formulas are:
dimethylamidoborane-bis-η5-cyclopentadienyl zirconium dichloride;
dimethylamidoborane-bis-η5-cyclopentadienyl zirconium dimethyl;
dimethylamidoborane-bis-η5-cyclopentadienyl zirconium bis-dimethylamide;
dimethylamidoborane-bis-η5-cyclopentadieny! zirconium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-η5-cyclopentadienyl zirconium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-η5-cyclopentadienyl zirconium 2-N.N-dimethylaminobenzyl;
dimethylamidoborane-bis-η5-cyclopentadienyl zirconium allyl;
dimethylamidoborane-bis-η5-cyclopentadienyl zirconium Η4-1 ,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-η5-cyclopentadienyl zirconium η4-2,4-hexadiene;
dimethylamidoborane-bis-η5-cyclopentadienyl zirconium η4-1 ,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-η5-cyclopentadienyl zirconium η4-1 -phenyl-1.3-pentadiene;
dimethylamidoborane-bis-η5-cyclopentadienyl zirconium η5-1 ,3-pentadiene;
dimethylamidoborane-bis-η5-n-butylcyclopentadienyl zirconium dichloride;
dimethylamidoborane-bis-η5-n-butylcyclopentadienyl zirconium dimethyl;
dimethylamidoborane-bis-η5-n-butylcyclopentadienyl zirconium bis-dimethylamide;
dimethylamidoborane-bis-η5-n-butylcyclopentadienyl zirconium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-η5-n-burylcyclopentadienyl zirconium 2,3-dimethyl-1,3-butadiene;

dimethylamidoborane-bis-η5-n-butylcyclopentadienyl zirconium 2-N.N-dimethylaminobenzyl;
dimethylamidoborane-bis-η5-n-butylcyclopentadienyl zirconium allyl;
dimethylamidoborane-bis-η5-n-butylcyclopentadienyl zirconium η4-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-η5-n-butylcyclopentadienyl zirconium η4-2,4-hexadiene;
dimethylamidoborane-bis-η5-n-butylcyclopentadienyl zirconium η4-1,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-η5-n-butylcyclopentadienyl zirconium η4-1 -phenyl-1,3-pentadiene;
dimethylamidoborane-bis-η5-n-butylcyclopentadienyl zirconium η5-1,3-pentadiene;
dimethylamidoborane-bis-η5-inden-1 -ylzirconium dichloride;
dimethylamidoborane-bis-η5-inden-1 -ylzirconium dimethyl;
dimethylamidoborane-bis-η5-indei>1 -ylzirconium bis-dimethylamide;
dimethylamidoborane-bis-η5-inden-1 -ylzirconium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-η5-inden-1 -ylzirconium 2,3-dimethyl-1,3-butadiene;
dimethyiamidoborane-bis-η5-inden-1 -ylzirconium 2-N,N-dimethylaminobenzyl;
dimethylamidoborane-bis-η5-inden-1 -ylzirconium ally);
dimethylamidoborane-bis-η5-inden-1 -ylzirconium η4-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-η5-inden-1 -ylzirconium η4-2.4-hexadiene;
dimethylamidoborane-bis-η5-inden-1 -ylzirconium η4-1,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-η5-inden-1 -ylzirconium η4-1-phenyl-1,3-pentadiene;
dimethylamidoborane-bis-η5-inden-1 -ylzirconium η4-1,3-pentadiene;
dimethylamidoborane-bis-n5-(2-methylinden-1-yl)zirconium dichloride; dimethylamidoborane-bis-η5-(2-methylinden-1-yl)zirconium dimethyl; dimethylamidoborane-bis-n5-(2-methylinden-1-yl)zirconium bis-dimethylamide; dimethylamidoborane-bis-η5-(2-methylinden-1 -yl)zirconium 2-methyl-1,3-butadiene;

dimethylamidoborane-bis-η5-(2-methylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-methylinden-1-yl)zirconium 2-N.N-• dimethylaminobenzyl;
dimethylamidoborane-bis-η5-(2-methylinden-1-yl)zirconium allyl;
dimethyiarnidoborane bis-η5-(2-methylinden-1-yl)zirconium η4"i,4-cfiphenyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-methylinden-1 -y\)zirconium η4-2,4-hexadiene;
dimethylamidoborane-bis-η5-(2-fnethylinden-1-yl)zirconium Ti4-1,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-methylindeiv1 -yl)zirconium η4-1 -phenyl-1,3-pentadiene;
dimethylamidoborane-bis-η5-(2-methylinden-1-yl)zirconium η4-1,3-pentadiene;
dimethylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium dichloride;
dimethylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium dimethyl;
dimethylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium bis-dimethylamide;
dimethylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;
dimethylamidoborane-bis-η5-(2-rnethyl-4-phenylinden-1-yl)zirconium allyl;
dimethylamidoborane-bis-η5-(2-methyl~4-phenylinden-1 -yl)zirconium η4-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium η4-2,4-hexadiene;
dimethylamidoborane-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium η4-1,4-
dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium η4-1-
phenyl-1,3-pentadiene;

dimethylamidoborane-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium η4-1,3-pentadiene;
dimethylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1 -yl)zirconium dichloride; dimethylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1-yl)zirconium dimethyl;
dimethylamidoborane-bis-η5(2-ethyl-4-phenylinden-1 -yl)zirconium bis-dimethylamide;
dimethylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1-yl)zirconium 2-N.N-dimethylaminobenzyl;
dimethylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1-yl)zirconium allyl;
dimethylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1-yl)zirconium η4-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-η5-{2-ethyl-4-phenylinden-1-yl)zirconium η4-2,4-hexadiene;
dimethylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1 -yl)zirconium η4-1.4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1-yl)zirconium η4-1-phenyl-1,3-pentadiene;
dimethylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1 -yl)zirconium η4-1,3-pentadiene;
dimethylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1 -yl)zirconium dichloride;
dimethylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1-yl)zirconium dimethyl;
dimethylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1-yl)zirconium bis-dimethylamide;
dimethylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-l-yl)zirconium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;

dimethylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1-yl)zirconium 2-N.N-dimethylaminobenzyl;
dimethylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1-yl)zirconium allyl;
dimethylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1 -yl)zirconium η4-1.4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1-yl)zirconium η4-2,4-hexadiene;
dimethylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1 -yl)zirconium η4-1 ,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1 -yl)zirconium η4-1 -phenyl-1,3-pentadiene;
dimethylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1 -yl)zirconium η4-1,3 pentadiene;
dimethylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium dichloride;
dimethylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium dimethyl;
dimethylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium bis-dimethylamide;
dimethylamidoborane-bis-η5-(2-nnethyl-4"naphthylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-methyl-4"naphthylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium 2-N.N-dimethylaminobenzyl;
dimethylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium allyl;
dimethylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1 -yl)zirconium η4-1 ,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium η4-2,4-hexadiene;
dimethylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1 -yl)zirconium η4-1,4-
dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1 -yl)zirconium η4-1 -
phenyl-1,3-pentadiene;

dimethylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1 -y!)zirconium η4 ,3-pentadiene;
dimethylamidoborane-bis-η5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yI)zirconium dichloride;
dimethylamidoborane-bis-η5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium dimethyl;
dimethylamidoborane-bis-η5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium bis-dimethylamide;
dimethylamidoborane-bis-η5-(2-methyl-4-bis(3,5-trifluoromethy1)phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
dimethylamidoborane-bis-η5-(2-methyl-4-bis(3,5-trifluoromethyl)phenyiinden-1-yl)zirconium allyl;
dimethylamidoborane-bis-η5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium η4-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-methy1-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium η4-2,4~hexadiene;
dimethylamidoborane-bis-η5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1 -yl)zirconium Η4-1 ,4-dinaphthyM ,3-butadiene;
dimethylamidoborane-bis-η5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium η4-1-phenyl-1,3-pentadiene;
dimethylamidoborane-bis-η5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium Η4-1 ,3-pentadiene;
dimethylamidoborane-bis-η5-(2-ethyl-4-bis(3,5-trifluoromethy1)phenylinden-1-yl)zirconium dichloride;
dimethylamidoborane-bis-η5-(2-ethyl-4-bis(3f5-trifluoromethyl)phenylinden-1-yl)zirconium dimethyl;
dimethylamidoborane-bis-η5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium bis-dimethylamide;

dimethylamidoborane-bis-η5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiunr> 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium 2,3-dimethyM ,3-butadiene;
dimethylamidoborane-bis-η5-(2-ethyl-4-bis(3l5-trifluoromethyl)phenylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
dimethylamidoborane-bis-η5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-y\)z\rconium allyl;
dimethylamidoborane-bis-η5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium Η4-1 ,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium η4-2,4-hexadiene;
dimethylamidoborane-bis-η5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yt)zirconium Η4-1 ,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium η4-1 -phenyl-1,3-pentadiene;
dimethylamidoborane-bis-η5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium η4-1,3-pentadiene;
dimethylamidoborane-bis-η5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1 -yl)zirconium dichloride;
dimethylamidoborane-bis-η5 -(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium dimethyl;
dimethylamidoborane-bis-η5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1 -yl)zirconium bis-dimethylamide;
dimethylamidoborane-bis-η5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1 -yl)zirconium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1 -yl)zirconium 2,3dimethyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-isopropyl-4-bis(315-trifluoromethyl)phenylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
dimethylamidoborane-bis-η5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1 -yl)zirconium allyl;

dimethylamidoborane-bis-η5-(2-isopropyl-4-bis(3>5-trifluoromethyl)phenylinden-1-yl)zirconium Η4-1 ,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-isopropyl-4-bis(3.5-trifluoromethyl)phenylinden-1 -yl)zirconium η4-2,4-hexadiene;
dimethylamidoborane-bis-η5-(2-isopropyl-4-bis(3.5-trifluoromethyl)phenyhnden-1-yl)zirconium η4-1,4-dinaphthyl-1.3-butadiene;
dimethylamidoborane-bis-η5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium η4-1-phenyl-1,3-pentadiene;
dimethylamidoborane-bis-η5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1 -yl)zirconium η4*-1,3-pentadiene;
dimethylamidoborane-bis-η5-(3-isopropylinden-1-yl)zirconiumdichloride;
dimethylamidoborane-bis-η5-(3-isopropyIinden-1 -yl)zirconium dimethyl;
dimethylamidoborane-bis-η5-(3-isopropylinden-1-yl)zirconium bis-dimethylamide;
dimethylamidoborane-bis-η5-(3-isopropylinden-1 -yl)zirconium 2-methy1-1,3-butadiene;
dimethylamidoborane-bis-η5-(3-isopropylinden-1 -yl)zirconium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(3-isopropylinden-1-yl)zirconJum 2-N.N-dimethylaminobenzyl;
dimethylamidoborane-bis-η5-(3-isopropylinden-1-yl)zirconium allyl;
dimethylamidoborane-bis-η5-(3-isopropylinden-1 -yl)zirconium η4-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(3-isopropylinden-1-yl)zirconium Η4-2,4-hexadiene;
dimethylamidoborane-bis-η5-(3-isopropylinden-1 -yl)zirconium Η4-1 ,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(3-isopropylinden-1 -yl)zirconium Η4-1 -phenyl-1,3-pentadiene;
dimethylamidoborane-bis-η5-(3-isopropylinden-1 -yl)zirconium Η4-1 ,3-pentadiene;
dimethylamidoborane-bis-η5-(3-t-butylinden-1 -yl)zirconium dichloride;

dimethylamidoborane-bis-η5-(3-t-butylinden-1 -yl)zirconium dimethyl;
dimethy}amidoborane"bis-η5-(3-t-butylinden-1 -y1)zircoriium bis-dimethylamide;
dimethylamidoborane-bis-η5-(3-t-butylinden-1 -yl)zirconium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(3-t-butylinden-1 -yl)zirconium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(3-t-butylinden-1-yl)zJrconium 2-N.N-dimethylaminobenzyl;
dimethylamidoborane-bis-η5-(3-t-butylinden-1-yl)zirconium allyl;
dimethylamidoborane-bis-η5-(3-t-butylinden-1-yl)zirconium η4-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(3-t"butylinden-1-yl)zirconium η4-2,4-hexadiene;
dimethylamidoborane-bis-η5-(3-t-butylinden-l -yI)zirconium η4-1,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(3-t-butylinden-1-yl)zirconium Η4-1 -phenyl-1,3-pentadiene;
dimethylamidoborane-bis-η5-(3-t-butylinden-1-yl)zirconium η4-1,3~pentadiene;
diisopropyiamidoborane-bis-η5-cyclopentadienylzirconium dichloride;
diisopropylamidoborane-bis-η5-cyclopentadienylzirconium dimethyl;
diisopropylamidoborane-bis-η5-cyclopentadienylzirconium bis-dimethylamide;
diisopropylamidoborane-bis-η5-cyclopentadieny!zirconium 2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-cyclopentadienylzirconium 2,3-dimethyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-cyc)operifadienylzirconium 2-N,N-dirnethylaminobenzyl;
diisopropylamidoborane-bis-η5-cyclopentadienylzirconium allyl;
diisopropylamidoborane-bis-η5-cyclopentadienylzirconium η4-1,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-cyclopentadienylzirconium η4-2,4-hexadiene;
diisopropylamidoborane-bis-η5-cyclopentadienylzirconium Η4- 1,4-dinaphthyl-1,3-butadiene;

diisopropylamidoborane-bis-η5-cyclopentadienylzirconium η4-1 -phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-η5-cyclopentadienylzirconium η5-1,3-pentadiene;
diisopropylamidoborane-bis-η5-inden-1 -ylzirconium dichloride;
diisopropylamidoborane-bis-η5-inden-1 -ylzirconium dimethyl;
diisopropylamidoborane-bis-η5-inden-1-ylzirconium bis-dimethylamide;
diisopropylamidoborane-bis-η5-inden-1 -ylzirconium 2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-inden-1 -ylzirconium 2,3-dimethyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-inden-1 -ylzirconium 2-N.N-dimethylaminobenzyl;
diisopropylamidoborane-bis-η5-inden-1 -ylzirconium allyl;
diisopropylamidoborane-bis-η5-inden-1 -ylzirconium η4-1,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-inden-1-ylzirconium η4-244-hexadiene;
diisopropylamidoborane-bis-η5-inden-1 -ylzirconium η4-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-inden-1 -ylzirconium η4"1 -phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-η5-inden-1 -ylzirconium η4-1,3-pentadiene;
diisopropylamidoborane-bis-η5-{2-methylrnden-1-yl)zirconium dichloride;
diisopropylamidoborane-bis-η5-(2-methylinden-1-yl)zirconium dimethyl;
diisopropy!amidoborane-bis-η5-(2-methylinden-1-yl)zirconium bis-dimethylamide;
diisopropylamidoborane-bis-η5-(2-methylinden-1 -yl)zirconium 2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-methylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-methylinden-1-yl)zirconium 2-N.N-dimethylaminobenzyl;
diisopropylamidoborane-bis-η5-(2-methylinden-1-yl)zirconium allyl;

diisopropylamidoborane-bis-η5-(2-methylinden-1 -yl)zirconium η4-1,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-methylinden-1-yl)zirconium Η4-2,4-hexadiene;
diisopropylamidoborane-bis-η5-(2-methylinden-1-yl)2irconium η4-1,4-dinapbthyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-methylinden-1-yl)zirconium η4-1-phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-η5-(2-methylinden-1 -yl)zirconium η4-1,3-pentadiene;
diisopropylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium dichloride;
diisopropylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium dimethyl;
diisopropylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium bis-dimethylamide;
diisopropylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-{2-methyl-4-phenylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium 2-N.N-dimethylaminobenzyl;
diisopropylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium allyl;
diisopropylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium Η4-1,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium η4-2,4-hexadiene;
diisopropylamidoborane-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium Η4-1 ,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconiurm η4-1-phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium Η4-1 ,3-pentadiene;

diisopropylamicloborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium dichloride;
diisopropylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yi)zirconium dimethyl;
diisopropylamidoborane-bis-η5-(2-methyl-4-naphthylinoen-1 -yi)zirconium bis-dimethylamide;
diisopropylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1 -yl)zirconium 2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1 -yl)zirconium 2,3-dimethyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium 2-N.N-dimethylaminobenzyl;
diisopropylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium allyl;
diisopropylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium Η4-1,4-diphenyl-1,3-butadiene;
diisopropy!amidoborane-bis-η5-(2-methyl-4-naphthylinden-1 -yl)zirconium η4-2,4-hexadiene;
diisopropylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium Η4-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-methyi-4-naphthylinden-1-yl)zirconium Η4-1-phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium η4-1,3-pentadiene;
diisopropylamidoborane-bis-η5-(2-methyl-4-(3,5-dimethylphenyl)inden-1-
yl)zirconium dichloride;
diisopropylamidoborane-bis-η5-(2-methyl-(3,5-dimethylphenyl)inden-1-
yl)zirconium dimethyl;
diisopropylamidoborane-bis-η5-(2-methyl-4-(3,5-dimethylphenyl)inden-1-yl)zirconium bis-dimethylamide;
diisopropylamidoborane-bis-η5-(2-methyl-4-(3,5-dimethylphenyl)inden-1-yl)zirconium 2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-methyl-4-(3,5-dimethylphenyl)inden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;

diisopropylamidoborane-bis-η5-(2-methy|-4-(3,5-dimethylphenyl)inden-1-y}} zirconium 2-N, N-dimethylaminobenzy);
diisopropylamidoborane-bis-η5-(2-rnethy|-4-(3,5-dimethylphenyl)inden-1-yl)zirconium allyl;
diisopropylamidoborane-bis-η5-(2-methy|-4-(3>5-cjjmethylphenyl)inden-1-yl)zirconium η4-1 ,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-methy|-4-(3,5-dimethylphenyl)inden-1-yl)zirconium η4-2,4-hexadiene;
diisopropylamidoborane-bis-η5-(2-methy|-4-(3.5-dimethylphenyl)inden-1-yl)zirconium η4-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-methyl-4-(3.5-dimethylphenyl)inden-1-yl)zirconium η4-1-phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-η5-(2-methy|-4-(3,5-dimethylphenyl)inden-1-yf) zirconium η4- T ,3-penfadiene;
diisopropylamidoborane-bis-η5-(2-methy|-4-(3,5-difluoromethylphenyl)inden-1-yl)zirconium dichloride;
diisopropylamidoborane-bis-η5-(2-methy|-4-(3,5-difiuoromethylphenyi)inden-1-yl)zirconium dimethyl;
diisopropylamidoborane-bis-η5-(2-methy|-4-(3,5-difluoromethylphenyl)inden-1-yl)zirconium bis-dimethylamide;
diisopropylamidoborane-bis-η5-(2-methy|-4.(3i5-clifluoromethylphenyl)inden-1-yl)zirconium 2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-methyi-4.(3i5-ciifluoromethylphenyl)inden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
diisoprapylamdabarane-b(s-η5"(2-(uethY diisopropylamidoborane-bis-η5-(2-methy|-4.(3,5-ciifluoromethylphenyl)inden-1-yl)zirconium allyl;
diisopropylamidoborane-bis-η5-(2-methy|-4-(3.5-difluoromethylphenyl)inden-1-yl)zirconium Η4-1 ,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-methy|-4-(3!5-difluoromethylphenyl)inden-1-yl)zirconium η4-2,4-hexadiene;

diisopropylamidoborane-bis-η5-(2-methyl-4-(3,5-difluoromethylphenyl)inden-1-yl)zirconium η4-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-methyl-4-(3,5-difluoronnethylphenyl)inden-1-yl)zirconium η4-1-phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-η5-(2-methyl-4-(3,5-difluoromethylphenyl)inden" 1 -yl)zirconium η4-1,3-pentadiene;
(zirconium dimethyl; (zirconium bis-
izirconium 2-
izirconium 2,3-
izirconium 2-N.N-
izirconium allyl; izirconium η4-1,4-
izirconium η4-2,4-
izirconium η4-1,4-
izirconium Η4-1-
izirconium η4-1,3-
diisopropy!amidoborane-bis-η5-(2-ethyl-4-phenylinden-1-yl)zirconium dichloride;
diisopropylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1 -yl
diisopropylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1-yl dimethylamide;
diisopropylamidoborane-bis-η5-(2-ethy!-4-phenylinden-1-yl methyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1-yl dimethyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1-yl dimethylaminobenzyl;
diisopropylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1-yl
diisopropylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1-yl diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1-yl hexadiene;
diisopropylamidoborane-bis-η5-(2-ethyl-4~phenylinden-1-yl dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1-yl phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1-yl pentadiene;diisopropylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1-yl)zirconium dichloride;
diisopropylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1-yl)zirconium dimethyl;

diisopropylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1-yl)zirconium bis-dimethylamide;
diisopropylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1-yl)zirconium 2-N.N-dimelhylaminobenzyl;
diisopropylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1-yl)zirconium allyl;
diisopropylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1-yl)zirconiumη4-1,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1-yl)zirconium Η4-2,4-hexadiene;
diisopropylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1-yl)zirconium η4-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1 -yl)zirconium η4-1 -phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1-yl)zirconium η4-1,3-pentadiene;
diisopropylamidoborane-bis-η5-(3-isopropyiinden-1-yl)zirconium dichloride;
diisopropylamidoborane-bis-η5-(3-isopropylinden-1-yl)zirconium dimethyl;
diisopropylamidoborane-bis-η5-(3-isopropylinden-1-yl)zirconium bis-dimethylamide;
diisopropylamidoborane-bis-η5-(3-isopropylinden-1 -yl)zirconium 2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(3-isopropylinden-1-yl)zirconium 2,3-dimethyl-1.3-butadiene;
diisopropylamidoborane-bis-η5-(3-isopropylinden-1-yl)zirconium 2-N.N-dimethylaminobenzyl;
diisopropylamidoborane-bis-η5-(3-isopropylinden-1-yl)zirconium allyl;
diisopropy\amidoborane-bis-η5-(3-isopropylinden-1 -yl)zirconium η4-1,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(3-isopropylinden-1-yl)zirconiumη4-2,4-
hexadiene;

diisopropylamidoborane-bis-η5-(3-isopropylinden-1 -yl)zirconium η4-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(3-isopropylinden-1-yl)zirconium η4-1-phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-η5-(3-isopropylinden-1-yl)zirconium η4-1.3-pentadiene;
diisopropylamidoborane-bis-η5-(3-t-butylinden-1 -yl)zirconium dichloride;
diisopropylamidoborane-bis-η5-(3-t-butylinden-1-yl)zirconium dimethyl;
diisopropylamidoborane-bis-η5-(3-t-butylinden-1-yl)zirconium bis-dimethylamide;
diisopropylamidoborane-bis-η5-(3-t-butylinden-1 -yl)zirconium 2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(3-t-butylinden-1 -yl)zirconium 2,3-dimethyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(3-t-butylinden-1-yl)zirconium 2-N.N-dimethylaminobenzyl;
diisopropylamidoborane-bis-η5-(3-t-butylinden-1-yl)zirconium allyl;
diisopropylamidoborane-bis-η5-(3-t-butylinden-1 -yl)zirconium η4-1,4-diphenyl-1,3-butadiene;
diiopropylamidoborane-bis-η5-(3-t-butylinden-1-yl)zirconium η4-2,4-hexadiene;
diisopropylamidoborane-bis-η5-(3-t-butylinden-1 -yl)zirconium η4-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(3-t-butylinden-1-yl)zirconium η4-1-phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-η5-(3-t-butylinden-1 -yl)zirconium η4-1,3-pentadiene;
diphenylamidoborane-bis-η5-cyclopentadienyl zirconium dichloride; diphenylamidoborane-bis-η5-cyclopentadienyl zirconium dimethyl; diphenylamidoborane-bis-η5-cyclopentadienyl zirconium bis-dimethylamide; diphenylamidoborane-bis-η5-cyclopentadieny! zirconium 2-methyl,3-butadiene;

diphenylamidoborane-bis-η5-cyclopentadienyl zirconium 2,3-dimethyl-l ,3-bufadiene;
diphenylamidoborane-bis-η5-cyclopentadienyl zirconium 2-N,N-dimethylaminobenzyl;
diphenylamidoborane-bis-η5-cyclopentadienyl zirconium allyl;
diphenylamidoborane-bis-η5-cyclopentadienyl zirconium η4-1,4-diphenyM ,3-butadiene;
diphenylamidoborane-bis-η5-cyclopentadienyl zirconium η4-2,4-hexadiene;
diphenylamidoborane-bis-η5-cyclopentadienyl zirconium η4-l ,4-dinaphthyl-1,3-butadiene;
diphenylamidoborane-bis-η5-cyclopentadienyl zirconium Η4-1 -phenyl-1,3-pentadiene;
diphenylamidoborane-bis-η5-cyclopentadienyl zirconium Η5-1 ,3-pentadiene;
diphenylamidoborane-bis-η5-n-butylcyclopentadienyl zirconium dichloride;
diphenylamidoborane-bis-η5-n-butylcyclopentadienyl zirconium dimethyl;
diphenylamidoborane-bis-η5-n-butylcyclopentadienyl zirconium bis-dimethylamide;
diphenylamidoborane-bis-η5-n-butylcyclopentadienyl zirconium 2-methyl-1,3-butadiene;
diphenylamidoborane-bis-η5-n-butylcyclopentadienyl zirconium 2,3-dimethyl-1,3-butadiene;
diphenylamidoborane-bis-η5-n-butylcyclopentadienyl zirconium 2-N.N-dimethylaminobenzyl;
diphenylamidoborane-bis-η5-n-butylcyclopentadienyl zirconium allyl;
dipheny)amidoborane-bis-η5-n-buty)cyclopentadienyl zirconium η4-1,4-diphenyl-1,3-butadiene;
diphenylamidoborane-bis-η5-n-butylcyclopentadienyl zirconium η4-2,4-hexadiene;
diphenylamidoborane-bis-η5-n-butylcyclopentadienyl zirconium Η4-1 ,4-dinaphthyl-l ,3-butadiene;
diphenylamidoborane-bis-η5-n-butylcyclopentadienyl zirconium η4-1 -phenyl-1,3-pentadiene;

diphenylamidoborane-bis-η5-n-butylcyclopentadienyl zirconium Η5-1 ,3-pentadiene;
diphenylamidoborane-bis-η5-inden-1-ylzirconium dichloride;
diphenylamidoborane-bis-η5-inden-1-ylzirconium dimethyl;
diphenylamidoborane-bis-η5-inden-1-ylzirconium bis-dimethylamide;
diphenylamidoborane-bis-η5-inden-1 -ylzirconium 2-methyl-1,3-butadiene;
diphenylamidoborane-bis-η5-inden-1 -ylzirconium 2.3-dimethyl-1,3-butadiene;
diphenylamidoborane-bis-η5-inden-1-ylzirconium 2-N,N-dimethylaminobenzyl;
diphenylamidoborane-bis-η5-inden-1 -ylzirconium allyl;
diphenylamidoborane-bis-η5-inden-1 -ylzirconium Η4-1 ,4-diphenyl-1,3-butadiene;
diphenylamidoborane-bis-η5-inden-1-ylzirconium η4-2,4-hexadiene;
diphenylamidoborane-bis-η5-inden-1 -ylzirconium η4-1,4-dinaphthyl-1,3-butadiene;
diphenylamidoborane-bis-η5-inden-1 -ylzirconium η4-1 -phenyl-1,3-pentadiene;
diphenylamidoborane-bis-η5-inden-1-ylzirconium η4-1,3-pentadiene;
diphenylamidoborane-bis-η5-(2-methylinden-1-yl)zirconium dichloride;
diphenylamidoborane-bis-η5-(2-methylinden-1-yl)zirconium dimethyl;
diphenylamidoborane-bis-η5-(2-methylinden-1 -yl)zirconium bis-dimethylamide;
diphenylamidoborane-bis-η5-(2-methylinden-1 -yl)zirconium 2-methyl-1,3-butadiene;
diphenylamidoborane-bis-η5-(2-methylinden-1 -yl)zirconium 2,3-dimethyl-1,3-butadiene;
diphenylamidoborane-bis-η5-(2-methylinden-1 -yl)zirconium 2-N.N-dimethylaminobenzyl;
diphenylamidoborane-bis-η5-(2-methylinden-1 -yl)zirconium allyl;
diphenylamidoborane-bis-η5-(2-methylinden-1 -yl)zirconium Η4- 1,4-diphenyl-1,3-butadiene;
diphenylamidoborane-bis-η5-(2-methylinden-1 -yl)zirconium η4-2,4-hexadiene;
diphenylamidoborane-bis-η5-(2-methylinden-1 -yl)zirconium η4-1,4-dinaphthyl-1,3-butadiene;

diphenylamidoborane-bis-η5-(2-methylinden-1 -yl)zirconium η4-1 -phenyl-1,3-pentadiene;
diphenylamidoborane-bis-η5-(2-methylinden-1-yl)zirconium η4-1,3-pentadiene;
diphenylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium dichloride;
diphenylamidoborane-bis-η5-(2-methyl~4-phenylinden-1-yl)zirconium dimethyl;
diphenyiamidoborane-bis-η5-(2-methyi-4-pheny1inden-1-yl)zirconium bis-dimethylamide;
diphenylamidoborane-bis-η5-(2-methyi-4-pheny!inden-1 -y!)zirconium 2-methyl-1,3-butadiene;
diphenylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
diphenyiamidoborane-bis-η5-{2-methyl-4-phenyfinden-1 -yl)zirconium 2-N.N-dimethylaminobenzyl;
diphenylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium allyl;
diphenylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium Η4-1 ,4-diphenyl-1,3-butadiene;
diphenylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconiurn η4-2.4-hexadiene;
diphenylamidoborane-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium η4-1.4-dinaphthyl-1,3-butadiene;
diphenylamidoborane-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium η4-1 -phenyl-1,3-pentadiene;
diphenylamidoborane-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium η4-1 ,3-pentadiene;
diphenylamidoborane-bis-η5-(2-ethyl-4-pheny!inden-1-yl)zirconium dichloride;
diphenylamidoborane-bisη5-(2-ethyl-4-phenylinden-1 -yl)zirconium dimethyl;
diphenylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1 -yl)zirconium bis-dimethylamide;
diphenylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1 -yl)zirconium 2-methyl-1,3-butadiene;
diphenylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1 -yl)zirconium 2,3-dimethyl-1,3-butadiene;

diphenylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
diphenylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1-yl)zirconium allyl;
diphenylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1-yl)zirconium η4-1,4-diphenyl-1,3-butadiene;
diphenylamidoborane-bis-η5-(2-ethyl-4-phenyiinden-1 -yl)zirconium η4-2,4-hexadiene;
diphenylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1 -yl)zirconium η4-1 ,4-dinaphthyl-1,3-butadiene;
diphenylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1 -yl)zirconium Η4-1 -phenyl-1,3-pentadiene;
diphenylamidoborane-bis-η5-(2-ethyl-4-phenylinden-1 -yl)zirconium η4-1,3-pentadiene;
diphenylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1-yl dichloride;
diphenytamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1-yl dimethyl;
diphenylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1-yl dimethylamide;
diphenylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1-yl methyl-1,3-butadiene;
diphenylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1 -yl dimethyl-1,3-butadiene;
diphenylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1-yl dtmethylam inobenzyl;
diphenylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-l-yl
diphenylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1-yl diphenyl-1,3-butadiene;
diphenylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1 -yl hexadiene;
diphenylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1-yr dinaphthyl-1,3-butadiene;
diphenylamidoborane-bis-η5-(2-isopropyl-4-phenyli nden-1 -yl phenyl-1,3-pentadiene;

zirconium
zirconium
zirconium bis-
zirconium 2-
zirconium 2,3-
zirconium 2-N.N-
zirconium allyl; zirconium η4-1,4-
zirconium Η4-2,4-
zirconium Η4-1 ,4-
zirconium Η4-1-

diphenylamidoborane-bis-η5-(2-isopropyl-4-phenylinden-1 -yl)zirconium η4-1,3-pentadiene;
diphenylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium dichloride;
diphenylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconiurn dimethyl;
diphynylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)2irconium bis-dimethylamide;
diphenylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
diphenylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
diphenylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1 -yl)zirconium 2-N.N-dimethylaminobenzyl;
diphenylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium allyl;
diphenylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconiumη4-1,4-diphenyl-1,3-butadiene;
diphenylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconiumη4-2,4-hexadiene;
diphenylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium Η4-1,4-dinaphthyl-1,3-butadiene;
diphenylamidoborane-bisη5-(2-methyl-4-naphthylinden-1-yl)zirconiumη4-1-phenyl-1,3-pentadiene;
diphenylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium η4-1,3-pentadiene;
diphenylamidoborane-bis-η5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium dichloride;
dip(ienylamidoborane-bis-η5(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium dimethyl;
diphenylamidoborane-bis-η5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium bis-dimethylamide;
diphenylamidoborane-bis-η5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;

diphenylamidoborane-bis-η5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
diphenylamidoborane-bis-η5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
diphenylamidoborane-bis-η5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium allyl;
diphenylafnidoborane-bis-η5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium Η4-1 ,4-diphenyl-1,3-butadiene;
diphenylamidoborane-bis-η5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium η4-2,4-hexadiene;
diphenylamidoborane-bis-η5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium η4-1 ,4-dinaphthyl-1,3-butadiene;
diphenylamidoborane-bis-η5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium Η4-1 -phenyl-1,3-pentadiene;
diphenylamidoborane-bis-η5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium Η4-1 ,3-pentadiene;
diphenylamidoborane-bis-η5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium dichloride;
diphenylamidoborane-bis-η5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium dimethyl;
diphenylamidoborane-bis-η5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium bis-dimethylamide;
diphenylamidoborane-bis-η5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
diphenylamidoborane-bis-η5-(2-ethyl-4-bis(3.5-trifluoromethyl)phenylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
diphenyiamidoborane-bis-η5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
diphenylamidoborane-bis-η5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium allyl;
diphenylamidoborane-bis-η5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenyiinden-1-yl)zirconium η4-1,4-diphenyl-1,3-butadiene;

diphenylamidoborane-bis-η5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-y))zirconium η4-2A-hexadiene;
diphenylamidoborane-bis-η5-(2-ethyl-4-bis(3!5-trifluorornethyl)phenylinden-1-yl)zirconium η5-1,4-dinaphthyl-1,3-butadiene;
diphenylamidoborane-bis-η5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium η4-1 -phenyl-1,3-pentadiene;
diphenylamidoborane-bis-η5(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium Η4-1 ,3-pentadiene;
diphenylamidoborane-bis-η5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1 -yl)zirconium dichloride;
diphenylamidoborane-bis-η5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1 -yl)zirconium dimethyl;
diphenylamidoborane-bis-η5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1 -yl)zirconium bis-dimethylamide;
diphenylamidoborane-bis-η5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1 -yl)zirconium 2-methyl-1,3-butadiene;
diphenylamidoborane-bis-η5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1 -yl)zirconium 2,3-dimethyl-1,3-butadiene;
diphenylamidoborane-bis-η5-(2-isopropyl-4-bis(3.5-trifluoromethyl)phenylinden-1-yl)zirconium 2-N.N-dimethylaminobenzyl;
diphenylamidoborane-bis-η5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1 -yl)zirconium allyl;
diphenylamidoborane-bis-η5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1 -yl)zirconium η4-1,4-diphenyl-1,3-butadiene;
diphenylamidoborane-bis-η5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1 -yl)zirconium η4-2,4-hexadiene;
diphenylamidoborane-bis-η5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1 -yl)zirconium η4-1,4-dinaphthyl-1,3-butadiene;
diphenylamidoborane-bis-η5-(2-isopropyl-4-b(s(3,5-trifluoromethyl)phenylinden-1 -yl)zirconium η4-1 -phenyl-1,3-pentadiene;
diphenylamidoborane-bis-η5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1 -yl)zirconium η4-1,3-pentadiene;

diphenylamidoborane-bis-η5-diphenylamidoborane-bis-η5-diphenylamidoborane-bis-η5-
dimethylamide;
diphenylamidoborane-bis-η5-
butadiene;
diphenylamidoborane-bis-η5-
1,3-butadiene;
diphenylamidoborane-bis-η5
dimethylaminobenzyl;
diphenylamidoborane-bis-η5-diphenylamidoborane-bis-η5-
1,3-butadiene;
diphenylamidoborane-bis-η5-
hexadiene;
diphenylamidoborane-bis-η5-dinaphthyl-1,3-butadiene;
diphenylamidoborane-bis-η5-i pentadiene;
diphenylamidoborane-bis-η5 pentadiene;
diphenylamidoborane-bis-η5-diphenylamidoborane-bis-η5-diphenylamidoborane-bis-η5-diphenylamidoborane-bis-η5-
butadiene;
diphenylamidoborane-bis-η5-
butadiene;
diphenylamidoborane-bis-η5-
dimethylaminobenzyl;
diphenylamidoborane-bis-η5-diphenylamidoborane-bis-η5-
1,3-butadiene;

3-isopropylinden-1 -yl)zirconium dichloride; 3-isopropylinden-1 -yl)zirconium dimethyl; 3-isopropylinden-1 -yl)zirconium bis-
3-isopropylinden-1 -yl)zirconium 2-methyl-1,3-
3-isopropylinden-1 -yl)zirconium 2,3-dimethyl-
3-isopropylinden-1 -yl)zirconium 2-N.N-
3-isopropylinden-1 -yl)zirconium allyl; 3-isopropylinden-1-yl)zirconium Η4-1 ,4-diphenyl-
3-isopropylinden-1 -yl)zirconium η4-2,4-
3-isopropylinden-1-yl)zirconium η4-1 ,4-
3-isopropylinden-1-yl)zirconium η4-1-phenyl-1,3-
3-isopropylinden-1 -yl)zirconium η4-1,3-
3-t-butylinden-1-yl)zirconium dichloride; 3-t-butylinden-1 -yl)zirconium dimethyl; 3-t-butylinden-1 -yl)zirconium bis-dimethylamide; 3-t-butylinden-1-yl)zirconium 2-methyl-1,3-
3-t-butylinden-1-yl)zirconium 2.3-dimethyl-1,3-
3-t-butylinden-1 -yl)zirconium 2-N.N-
3-t-butylinden-1 -yl)zirconium allyl; 3-t-butylinden-1 -yl)zirconium η4-1 ,4-diphenyl-

diphenylamidoborane-bis-η5-(3-t-butylinden-1-yl)zirconiumη4-2,4-hexadiene;
diphenytemidoborane-bis-η5-(3-(-butyft"nden-1-yOzirconi"um η4-1,4-dinaphthyf-1,3-butadiene;
diphenylamidoborane-bis-η5-(3-t-butylinden-1 -yl)zirconium η4-1 -phenyl-1,3-pentadiene;
diphenylamidoborane-bis-η5-(3-t-butylinden-1 -y!)zirconium η4-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-η5-cyclopentadienyizirconiumdichloride;
bis(trimethylsilyl)amidoborane-bis-η5-cyclopentadienylzirconium dimethyl;
bis(trimethylsilyl)amidoborane-bis-η5-cyclopentadienylzirconiumbis-
dimethylamide;
bis(trimethylsilyl)amidoborane-bis-η5-cyclopentadienylzirconium2-methyl-1,3-butadiene;
bis(trimethy{sity{)amidoborane-bis-η5-cyciopentadieny{zirconium2,3-dimett\y(- 1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-cyclopentadienylzirconium2-N,N-dimethylaminobenzyl;
bis(trimethylsilyl)amidoborane-bis-η5-cyclopentadienylzirconium allyl;
bis(trimethylsilyl)amidoborane-bis-η5-cyclopentadienylzirconium η4-l,4- diphenyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-cyclopentadienyl2irconium η4-2.4-hexadiene;
bis(trimethylsilyl)amidoborane-bis-η5-cyclopentadienyl2irconium η4-1.4-
dinaphthyl-1,3-butadiene;
bis(trimethylsityl)amidoborane-bis-η5-cyclopentadienylzirconium Η4-1 -phenyl-
1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-η5-cyclopentadienylzirconium η5-1.3-pentadiene;
bis(trimethy!silyl)amidoborane-bis-η5-inclen-1-ylzirconiumdichloride; bis(trimethylsilyl)amidoborane-bis-η5-inden-1-ylzirconium dimethyl; bis(trimethylsilyl)amidoborane-bis-η5-incien-1-y!zirconium bis-dimethylamide; bis(trimethyisilyl)amidoborane-bis-η5-intlen-1 -ylzirconium 2-methyl-1,3-butadiene;

bis(trimethylsilyl)amidoborane-bis-η5-inden-1-ylzirconium 2,3-dimethyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-inden-1-ylzirconium 2-N.N-dimethylaminobenzyl;
bis(trimethylsilyl)amidoborane-bis-η5-inden-1-ylzirconium allyl;
bis(trimethylsilyl)amidoborane-bis-η5-inden-1-y!zirconium Η4-1 ,4-diphenyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-inden-1-ylzirconium η4-2.4-hexadiene;
bis(trimethylsilyl)amidoborane-bis-η5-inden-1 -ylzirconium η4-1,4-dinaphthyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-inden-1 -ylzirconium Η4-1 -phenyl-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-η5-inden-1 -ylzirconium Η4-1 ,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methylinden-1-yl)zirconiumdichloride; bis(trimethylsilyl)amidoborane-bis-η5-(2-methylinden-1-yl)zirconium dimethyl; bis(trimethylsilyl)amidoborane-bis-η5-(2-methylinden-1-yl)zirconiumbis-
dimethylamide;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methylinden-1-yl)zirconium2-methyl-
1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methylinden-1-yl)zirconium2,3-
dimethyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-{2-methylinden-1-yl)zirconium2-N,N-
dimethylaminobenzyl;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methylinden-1-yl)zirconium allyl;
bis(trimethy!silyl)amidoborane-bis-η5-(2-methylinden-1 -yl)zirconium η4- ,4-
diphenyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methylinden-1-yl)zirconium η4,-2,4-
hexadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methylinden-1 -yl)zirconium Η4-1 ,4-
dinaphthyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methylinden-1 -yl)zirconium η4--1-
phenyl-1,3-pentadiene;

bis(trimethylsilyl)amidoborane-bis-η5-(2-methylinden-1 -yl)zirconium η4-1.3-pentadiene;
bis(trimethylsilyl)arnidoborane-bis-η5-(2-melhyl-4-phenylinden-1-yl)zirconium dichloride;
bis(trimethylsilyl)amidoborane-bisη5-(2-methyl-4-pheny»inden-1-yl)zirconium dimethyl;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methyl-4-ph6nylinden-1-yl)zirconium bis-dimethylamide;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methyJ-4-phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
bis(trimethylsilyl)amidoborane-bis-η5-{2-methyl-4-phenylinden-1-yl)zirconium allyl;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methyl-4-phenyIinden-1-yl)zirconium η4-1,4-diphenyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium η4-2,4-hexadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methyl-4-phenyitnden-1-yl)zirconium Η4-1 ,4-dinaphthyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium η4-1 -phenyl-1,3-pentadiene;
bis{trimethylsilyl)amidoborane-bis-η5-(2-methyl-4-phenyiinden-1-yl)zirconium η4-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium dichloride;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium dimethyl;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium bis-dimethylamide;

bis(trimethylsilyl)amidoborane-bis-η5-{2-methyl-4-naphthylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium allyl;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium η4-1,4-diphenyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium η4-2,4-hexadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methyl-4-naphthylinden-1-y1)zirconium η4-1,4-dinaphthyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium
η4-1 -phenyl-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium
η4-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(3-isopropylinden-1-yl)zirconium
dichloride;
bis(trimethylsilyl)amidoborane-bis-η5-(3-isopropylinden-1-yl)zirconium
dimethyl;
bis(trimethylsilyl)amidoborane-bis-η5-(3-isopropylinden-1-yl)zirconiumbis-
dimethylamide;
bis(trimethyisilyl)amidoborane-bis-η5-(3-isopropylinden-1-yl)zirconium 2-
methyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(3-isopropylinden-1-yl)zirconium 2,3-
dimethyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(3-isopropylinden-1-yl)zirconium 2-N,N-
dimethylaminobenzyl;
bis(trimethylsilyl)amidoborane-bis-η5-(3-isopropylinden-1-yl)zirconium allyl;
bis(trimethylsilyl)amidoborane-bis-η5-(3-isopropylinden-1 -yl)zirconium η4-1 ,4-diphenyl-1,3-butadiene;

bis(trimethylsilyl)amidoborane-bis-η5-(3-isopropylinden-1 -yl)zirconium η4-2,4-hexadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(3-isopropyiinden-1 -yl)zirconium η4-1 ,4-dinaphthyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(3-isopropylinden-1 -yl)zirconium η4-1 -phenyl-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(3-isopropylinden-1 -yl)zirconium η4-1 ,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(3-t-butylinden-1-yl)zirconium dichloride;
bis(trimethylsilyl)amidoborane-bis-η5-(3-t-butylinden-1-yl)zirconium dimethyl;
bis(trimethylsilyl)amidoborane-bis-η5-(3-t-butylinden-1-yl)zirconium bis-dirnethylamide;
bis(trimethylsilyl)amidoborane-bis-η5-(3-t-butylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(3-t-butylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(3-t-butylinden-1-yl)zirconium 2-N.N-dimethylaminobenzyl;
bis(trimethylsilyl)amidoborane-bis-η5-(3-t-butylinden-1-yl)zirconium allyl;
bis(trimethylsilyl)amidoborane-bis-η5-(3-t-butylinden-1 -yl)zirconium η4-1,4-diphenyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(3-t-butylinden-1-yl)zirconium η4-2,4-hexadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(3-t-butylinden-1 -yl)zirconium η4-1 ,4-dinaphthyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(3-t-butylinden-1-yl)zirconium η4-1-phenyl-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(3-t-butylinden-1 -yl)zirconium η4-1,3-pentadiene;
bis(diisopropylamido)diborane-1,2-bis-η5-(2-rnethyl-4-phenylinden-1 -yl)zirconium dichloride;
bis(diisopropylamido)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium dimethyl;

bis(diisopropylamido)diborane-1,2~bis-η5-(2-mefhyl-4-phenyl/nden-1 -yl)zirconium bis-dimethylamide;
bis(diisopropylamido)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
bis(diisopropylamido)diborane-1,2-bis-η5"(2-methyl-4-phenylinden-1 -yl)zirconium 2,3-dimethyl-1,3-butadiene;
bis(diisopropylamido)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;
bis(diisopropylamido)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium allyl;
bis(diisopropylamido)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium η4~1,4-diphenyl-1,3-butadiene;
bis(diisopropylamido)diborane-1,2-bis-η5-(2-methyJ-4-pnenylinden-1 -yl)zirconium η4-2,4-hexadiene;
bis(diisopropylamido)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium η4-1 ,4-dinaphthyl-1,3-butadiene;
bis(diisopropylamido)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium Η4-1 -phenyl-1,3-pentadiene;
bis(diisopropylamido)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium Η4-1 ,3-pentadiene;
dimethylamidoborane-bis-η5-cyclopentadienyl hafnium dichloride;
dimethylamidoborane-bis-η5-cyclopentadienyl hafnium dimethyl;
dimethylamidoborane-bis-η5-cyclopentadienyl hafnium bis-dimethylamide;
dimethy(amidoborane-bis-η5-cydopentadteny( hafnium 2-methyI-1,3-butadiene;
dimethylamidoborane-bis-η5-cyclopentadienyi hafnium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-η5-cyclopentadienyl hafnium 2-N.N-dimethylaminobenzyl;
dimethylamidoborane-bis-η5-cyclopentadienyl hafnium allyl;
dimethylamidoborane-bis-η5-cyclopentadienyl hafnium η4-1 ,4-diphenyM,3-butadiene;
dimethylamidoborane-bis-η5-cyclopentadienyl hafnium η4-2,4-hexadiene;

dimethylamidoborane-bis-η5-cyclopentadienyl hafnium V-1,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-η5-cyclopentadienyl hafnium η4-1-phenyl-1,3-pentadiene;
dimethylamidoborane-bis-η5-cyclopentadieny! hafnium η5-1,3-pentadiene;
dimethylamidoborane-bis-η5-n-butylcyclopentadienyl hafnium dichloride;
dimethy)amidoborane-bis-η5-n-butylcyclopentadienyl hafnium dimethyl;
dimethylamidoborane-bis-η5-n-butylcyclopentadienyl hafnium bis-dimethylamide;
dimethylamidoborane-bis-η5-n-butylcyclopentadienyl hafnium 2-methyl-1,3-butadiene;
dimethyiamidoborane-bis-η5-n-butylcyclopentadienyl hafnium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-η5-n-butylcyclopentadienyl hafnium 2-N.N-dimethylaminobenzyl;
dimethylamidoborane-bis-η5-n-butylcyclopentadienyl hafnium allyl;
dimethylamidoborane-bis-η5-n-butylcyclopentadienyl hafnium η4-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-η5-n-butylcyclopentadienyl hafnium Η4-2,4-hexadiene;
dimethylamidoborane-bis-η5-n-butylcyclopentadienyl hafnium η4-1,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-η5-n-butylcyclopentadienyl hafnium η4-1 -phenyl-1,3-pentadiene;
dimethylarnidaborane-bis-η5-n-butylcyclopentadienyl hafnium η5-1 ,3-pentadiene;
dimethylamidoborane-bis-η5-inden-1 -ylhafnium dichloride; dimethylamidoborane-bis-η5-inden-1 -ylhafnium dimethyl; dimethylamidoborane-bis-η5-inden-1-ylhafnium bis-dimethylamide; dimethylamidoborane-bis-η5-inden-1 -ylhafnium 2-methyl-1,3-butadiene; dimethylamidoborane-bis-η5-inden-1 -ylhafnium 2,3-dimethyl-1,3-butadiene; dimethylamidoborane-bis-η5-inden-1 -ylhafnium 2-N.N-dimethytaminobenzyl;

dimethylamidoborane-bis-ri -inden-1 -ylhafnium allyl;
dimethylamidoborane-bis-η5-inden-1-ylhafnium η4-1,4-diphenyl-1,3-butadiene; dimethylamidoborane-bis-η5-inden-1 -ylhafnium η4-2,4-hexadiene; dimethylamidoborane-bis-η5-inden-1 -ylhafnium η4-1 ,4-dinaphthyl-l ,3-
butadiene;
dimethy!amidoborane-bis-η5-inden-1-ylhafnium η4-1 -phenyl- 1,3-pentadiene; dimethylamidoborane-bis-η5-inden-1 -ylhafnium η4-1,3-pentadiene;
dimethylamidoborane-bis-η5-(2-methylinden-1 -yl)hafnium dichloride;
dimethylamidoborane-bis-η5-(2-methylinden-1 -yl)hafnium dimethyl;
dimethylamidoborane-bis-η5-(2-methylinden-1-yl)hafnium bis-dimethylamide;
dimethyfamidoborane-bis-η5-(2-methylinden-1-yl)hafnium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-methylinden-1-yl)hafnium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-methylinden-l -yl)hafnium 2-N.N-dimethylaminobenzyl;
dimethylamidoborane-bis-η5-(2-methylinden-1 -yl)hafnium allyl;
dimethylamidoborane-bis-η5-(2-methylinden-1-yl)hafnium η4-1 ,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-methylinden-1-yl)hafnium η4-2,4-hexadiene;
dimethylamidoborane-bis-η5-(2-methylinden-1 -yl)hafnium η4-1,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-methylinden-l -yl)hafnium η4-1 -phenyl-1,3-pentadiene;
dimethylamidoborane-bis-η5-(2-methylinden-1 -yl)hafnium η4-1,3-pentadiene;
dimethylamidoborane-biS"η5-(2-methyl-4-phenylinden-1-yl)hafniunn dichloride;
dimethylamidoborane-bisη5-(2-methyl-4-phenylinden-1 -yl)hafnium dimethyl;
dimethylamidoborane-bisη5-(2-methyl-4-phenylinden-1-yl)hafnium bis-dimethylamide;
dimethylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)hafnium 2-methyl-1,3-butadiene;

dimethylamidoborane-bis-η5-^-methyM-phenylinden-1 -yl)hafniurn 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)hafnium 2-N.N-dimethylaminobenzyl;
dimethylamidoborane-bis-η5-(2-methyl-4-phenylinden-1 -yl)hafnium allyl;
dimethylamidoborane-bis-η5-(2-mernyl-4-phenylinden-1-yl)hafnium η4-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-η5-{2-methy!-4-phenylinden-1-yl)hafnium η4-2,4-hexadiene;
dimethylamidoborane-bis-η5-(2-methyl"4-phenylinden-1 -yl)hafnium η4-1 A-dinaphthyl-1,3-butadiene;
dimethylamidoborane*bis-η5-(2-methyl-4-phenylinden-1-yl)hafnium η4-1-phenyl-1,3-pentadiene;
dimethylamidoborane-bis-η5-(2-methyl-4-phenylinden-1 -yl)hafnium η4-1,3-pentadiene;
dimethylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)hafnium dichloride;
dimethylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)hafnium dimethyl;
dimethylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)hafniumbis-dimethylamide;
dimethylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1 -yl)hafnium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1 -yl)hafnium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)hafnium 2-N.N-
dimethylaminobenzyl;
dimethylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)hafnium allyl;
dimethylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)hafnium η4-1.4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)hafnium η4-2,4-hexadiene;
dimethylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1 -yl)hafnium η4-1,4-dinaphthyl-1,3-butadiene;

dimethylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-y|)hafnium η4-1-phenyl-1,3-pentadiene;
dimethylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)hafnium η4-1,3-pentadiene;
dimethylamidoborane-bis-η5"(3-isopropylinden-1-yl)hafnium dichloride;
dimethylamidoborane-bis-η5-(3-isopropylinden-1-yl)hafnium dimethyl;
dimethylamidoborane-bis-η5-(3-isopropylinden-1 -yl)hafnium bis-dimethylamide;
dimethylamidoborane-bis-η5-(3-isopropylinden-1 -yl)hafnium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(3-isopropylinder)-1 -yl)hafnium 2.3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(3-isopropylinden-1-yl)hafnium 2-N.N-dimethylaminobenzyl;
dimethylamidoborane-bis-η5-(3-isopropylinden-1-y!)hafnium allyl;
dimethylamidoborane-bis-η5-(3-isopropylinden-1-yl)hafniumη4-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(3-isopropylinden-1-yl)hafnium η4-2,4-hexadiene;
dimethylamidoborane-bis-η5-(3-isopropylinden-1 -yl)hafnium η4-1 ,4-dinaphthyl-1,3-butadiene;
dimethyiamidoborane-bis-η5-(3HSOpropylinden-1-yl)hafnium η4-1-pheny|-1,3-pentadiene;
dimethylamidoborane-bis-η5-(3-isopropy!inden-1 -yl)hafnium η4-1 ,3-pentadiene;
dimethylamidoborane-bis-η5-(3-t-butylinden-1-yl)hafnium dichloride;
dimethylamidoborane-bis-η5-{3-t-butylinden-1-yl)hafnium dimethyl;
dimethylamidoborane-bis-η5-(3-t-butylinden-1 -yl)hafnium bis-dimethylamide;
dimethylamidoborane-bis-η5-(3-t-butylinden-1 -yt)hafnium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(3-t-butylinden-1 -yl)hafnium 2,3-dimethyl-1,3-butadiene;

dimethylamidoborane-bis-η5-(3-t-butylinden-1 -yl)hafnium 2-N.N-dimethylaminobenzyl;
dimethylamidoborane-bis-η5-(3-t-butylinden-1 -yl)hafnium allyl;
dimethylamidoborane-bis-η5-(3-t-butylinden-1 -yl)hafnium η4-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(3-t-butylinden-1-yl)hafniumη4-2,4-hexadiene;
dimethylamidoborane-bis-η5-(3-t-butylinden-1 -yl)hafnium η4-1 ,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-η5-(3-t-butylinden-1 -yl)hafnium η4-1 -phenyl-1,3-pentadiene;
dimethylamidoborane-bis-η5-(3-t-butylinden-1-yl)hafnium η4-1.3-pentadiene;
diisopropylamidoborane-bis-η5-cyclopentadienylhafnium dichloride;
diisopropylamidoborane-bis-η5-cyclopentadienylhafnium dimethyl;
diisopropylamidoborane-bis-η5-cyclopentadienylhafnium bis-dimethylamide;
diisopropyiamidoborane-bis-η5-cyclopentadienylhafnium2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-cyclopentadienylhafnium 2,3-dimethyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-cyclopentadienylhafnium 2-N.N-dimethylaminobenzyl;
diisopropylamidoborane-bis-η5-cyclopentadienylhafnium allyl;
diisopropylamidoborane-bis-η5-cyclopentadienylhafnium η4-1,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-cyclopentadienylhafnium η4-2,4-hexadiene;
diisopropylamidoborane-bis-η5-cyclopentadienylhafnium η4-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-cyclopentadienylhafnium η4-1-phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-η5-cyclopentadienylhafnium η5-1,3-pentadiene;
diisopropylamidoborane-bis-η5-inden-1 -ylhafnium dichloride; diisopropylamidoborane-bis-η5-inden-1 -ylhafnium dimethyl; diisopropylamidoborane-bis-η5-inden-1-ylhafnium bis-dimethylamide;

dη5opropy!amidoborane-bis-η5-inden-1 -ylhafnium 2-methyl-1,3-butadiene;
dη5opropylamidoborane-bis-η5-inden-1-ylhafnium 2,3-dimethyl-1.3-butadiene;
dη5opropylamidoborane-bis-η5-inden-1 -ylhafnium 2-N,N-dimethylaminobenzyl;
dη5opropylamidoborane-bis-η5-inden-1 -ylhafnium allyl;
dη5opropylamidoborane-bis-η5-inden-1 -ylhafnium Η4-1 ,4-diphenyl-1,3-butadiene;
dη5opropylamidoborane-bis-η5-inden-1 -ylhafnium η4-2,4-hexadiene;
dη5opropylamidoborane-bis-η5-inden-1 -ylhafnium η4-1,4-dinaphthyl-1,3-butadiene;
dη5opropylamidoborane-bis-η5-inden-1 -ylhafnium η4-1 -phenyl-1,3-pentadiene;
dη5opropylamidoborane-bis-η5-inden-1 -ylhafnium η4-1,3-pentadiene;
dη5opropylamidoborane-bis-η5-(2-methylinden-1-yl)hafniumdichloride;
dη5opropylamidoborane-bis-η5-(2-methylinden-1-yl)hafnium dimethyl;
dη5opropylamidoborane-bis-η5-(2-methylinden-1 -yl)hafnium bis-dimethylamide;
dη5opropylamidoborane-bis-η5-{2-methylinden-1 -yl)hafnium 2-methyl-1.3-butadiene;
dη5opropylamidoborane-bis-η5-(2-methylinden-1 -yl)hafnium 2,3-dimethyl-1,3-butadiene;
dη5opropylamidoborane-bis-η5-(2-methylinden-1-yl)hafnium 2-N.N-dimethylaminobenzyl;
dη5opropylamidoborane-bis-η5-(2-methylinden-1-yl)hafnium allyl;
dη5opropylamidoborane-bis-η5-(2-methylinden-1 -yl)hafnium η4-1,4-diphenyl-1,3-butadiene;
dη5opropylamidoborane-bis-η5-(2-methylinden-1-yl)hafnium η4-2,4-hexadiene;
dη5opropylamidoborane-bis-η5-(2-methylinden-1 -yl)hafnium η4-l ,4-dinaphthyl-1,3-butadiene;
dη5opropylamidoborane-bis-η5-(2-methylinden-1 -yl)hafnium η4-1-phenyl-1,3-pentadiene;
dη5opropylamidoborane-bis-η5-(2-methylinden-1-yl)hafnium η4-1,3-pentadiene;

diisopropylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)hafnium dichloride;
diisopropylamidoborane-bis-η5-(2"methyl-4-phenylinden-1-yl)hafnium dimetti
diisopropylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)hafnium bis-dimethylamide;
diisopropylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)hafnium 2-methyt-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-methyJ-4-phenyJJnden-1-yl)hafnium 2,3-dimethyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-methyl-4-pheny!inden-1-yl)hafnium 2-N.N-dimethylaminobenzyl;
diisopropylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)hafnium allyl;
diisopropylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)hafnium η4-1,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)hafnium Η4-2,4-hexadiene;
diisopropylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)hafnium η4-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)hafnium η4-1-
phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-η5-(2-nriethyl-4-phenylinden-1-yl)hafnium η4-1,3-
pentadiene;
diisopropylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)hafnium
dichloride;
diisopropylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)hafnium
dimethyl;
diisopropylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)hafnium bis-
dimethylamide;
diisopropylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)hafnium 2-
methyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)hafnium 2,3-
dimethyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)hafnium 2-N,
dimethylaminobenzyt;

diisopropylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)hafnium allyl;
diisopropylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)hafnium η4-1.4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)hafnium η4-2,4-hexadiene;
diisopropylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1-ylihafnium η4-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(2-methyl-4-naphthyiinden-1-yl)hafnium Η4-1-phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-η5-(2-methyl-4-naphthylinden-1 -yl)hafnium Η4-1 ,3-pentadiene;
diisopropylamidoborane-bis-η5-(3-isopropylinden-1-yl)hafnium dichloride;
diisopropylamidoborane-bis-η5-(3-isopropylinden-1-yl)hafnium dimethyl;
diisopropylamidoborane-bis-η5-(3-isopropylinden-1-yl)hafnium bis-dimethylamide;
diisopropylamidoborane-bis-η5-(3-isopropylinden-1 -yl)hafnium 2-methyM ,3-butadiene;
diisopropylamidoborane-bis-η5-(3-isopropylinden-1-yl)hafnium 2,3-dimethyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(3-isopropylinden-1-y!)hafnium 2-N.N-dimethylaminobenzyl;
diisopropylamidoborane-bis-η5-(3-isopropylinden-1-yl)hafnium allyl;
diisopropylamidoborane-bis-η5-(3-isopropylinden-l -y|)hafnium Η41 ,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(3-isopropylinden-i-y|)hafnium η4 2,A-hexadiene;
diisopropylamidoborane-bis-η5-(3-isopropylinden-1 -yl)hafnium η4-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(3-isopropylinden-1 -yl)hafnium Η4-1 -phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-η5-(3-isopropylinden-1 -yl)hafnium Η4-1 ,3-pentadiene;
diisopropylamidoborane-bis-η5-( tylinden-1-yl)hafnium dichloride;

diisopropylamidoborane-bis-η5-(3-t-butylinden-l-yl)hafnium dimethyl;
diisopropylamidoborane-bis-η5-(3-t-butylinden- f -yl}hafnium bis-dimethylamide;
diisopropylamidoborane-bis-η5-(3-t-butylinden-1 -yl)hafnium 2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(3-t-butylinden-1 -yl)hafnium 2,3-dimethyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(3-t-butylinden-1-yl)hafnium 2-N.N-dimethylaminobenzyl;
diisopropylamidoborane-bis-η5-(3-t-butylinden-1 -yl)hafnium allyl;
diisopropylamidoborane-bis-η5-(3-t-butyIinden-1 -yl)hafnium TJ*-1 ,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(3-t-butylinden-1-yl)hafniumη4-2,4-hexadiene;
diisopropylamidoborane-bis-η5-(3-t-butylinden-1 -yl)hafnium η4-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-η5-(3-t-butylinden-1 -yl)hafnium Η4-1 -phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-η5-(3-t-butylinden-1-yl)hafnium η4-1,3-pentadiene;
bis(rimethylsilyl)amidoborane-bis-η5-cyclopentadienythafnium dichloride;
bis(trimethylsilyl)amidoborane-bis-η5-cyclopentadienylhafnium dimethyl;
bis(trimethylsilyl)amidoborane-bis-η5-cyclopentadienylhafnium bis-dimethylamide;
bis(trimethylsilyl)amidoborane-bis-η5-cyclopentadienylhafnium 2-methyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-cyclopentadienylhafnium 2,3-dimethyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-cyclopentadienylhafnium 2-N.N-dimethylaminobenzyl;
bis(trimethylsilyl)amidoborane-bis-η5-cyclopentadienylhafnium allyl;
bis(trimethylsilyl)amidoborane-bis-η5-cyclopentadienylhafnium η4-1,4-diphenyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-cyclopentadienylhafnium η4-2,4-hexadiene;

bis(trimethylsilyl)amidoborane-bis-η5-cyctopentadienylhanium η4-1,4-dinaphthyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-biS"η5-cyclopentadienylhafnium η4-1-phenyl-1,3-pentadiene;
bis(tnmethylsilyl)amidoborane-bis-η5, ;lopentadieny!hafniuum η5-1.3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-η5-inden-1-ylhafnium dichloride;
bis(trimethylsilyl)amidoborane-bis-η5-inden-1-ylhafnium dimethyl;
bis(trimethylsilyl)amidoborane-bis-η5-inden-1-ylhafnium bis-dimethylamide;
bis(trimethylsilyl)amidoborane-bis-η5-inden-1 -ylhafnium 2-methyl-1,3-butadiene;
bis(trimethyisilyl)amidoborane-bis-η5-inden-1 -ylhafnium 2,3-dimethyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-inden-1 -ylhafnium 2-N.N-dimethylaminobenzyl;
bis(trimethylsilyl)amidoborane-bis-η5-inden-1 -ylhafnium allyl;
bis(trimethylsilyl)amidoborane-bis-η5-inden-1-ylhafnium Η4-1 ,4-diphenyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-inden-1-ylhafnium η4-2,4-hexadiene;
bis(trimethylsilyl)amidoborane-bis-η5-inden-1-ylhafnium η4-1,4-dinaphthyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-inden-1 -ylhafnium η4-1 -phenyl-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-η5-inden-1 -ylhafnium η4-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methylinden-1-yl)hafnium dichloride;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methylinden-1-yi)hafnium dimethyl;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methylinden-l-yl)hafniumbis-dimethylamide;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methylinden-1-yl)hafntum2-methyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methylinden-1 -yl)haf nium 2,3-dimethyl- 1,3-butadiene;


bis(trimethy!silyl)amidoborane-bis-η5-(2-methylinden-1"yl)hafnium 2-N.N-dimethylaminobenzyl;
bis(trimethylsilyl)amidoborane-bis-η5-(2-methylinden-1-yl)hafniumallyl;
bis(trimethylsilyl)amidoborane-bis-η5-diphenyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-hexadiene;
bis(trimethylsilyl)amidoborane-bis-η5-dinaphthyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-η5-pentadiene;
bis(trimethylsilyl)amidoborane-bis-η5 dichloride;
bis(trimethyisilyl)amidoborane-bis-η5-dimethyl;
bis(trimethylsilyl)amidoborane-bis-η5-bis-dimethylamide;
bis(trimethylsilyl)amidoborane-bis-η5-methyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5 2.3-dimethyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5 N,N-dimethylaminoben2yl;
bis(trimethylsilyl)amidoborane-bis-η5-
allyl;
bis(trimethylsilyl)amidoborane-bis-η5 -1,4-diphenyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-2,4-hexadiene;
bis(trimethylsilyl)amidoborane-bis-η5-1,4-dinaphthyl-1,3-butadiene;
2-methylinden-1 -yl)hafnium η4-1,4-2-methylinden-1 -yl)hafnium ri"-2.4-2-methylinden-1 -yl)hafnium Η4-1.4-2-methylinden-1 -yl)hafnium η5- 1 -phenyl-2-methylinden-1 -yl)hafnium η4-"1,3-
2-methyl-4-phenylinden-1 -yl)haf nium 2-methyl-4-phenylinden-1-yl)hafnium 2-methyl-4-phenylinden-1 -yl)haf nium 2-methy!-4-phenytinden-1 -yl)hafnium 2-2-methyl-4-phenylinden-1-yl)hafnium 2-methyl-4-phenylinden-1 -yl)hafnium 2-2-methyl-4-phenylinden-1 -yl)hafnium 2-methyl-4-phenylinden-1 -yl)hafnium Η4-2-methyl-4-phenylinden-1 -yl)hafnium Η4-2-methyl-4-phenylinden-1 -yl)hafnium r\*-

1 -phenyl-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(2-"methy|-4-Pheny|inden-1 -yl)haf nium η4-1,3-pentadiene;
bis(tnmethylsilyl)amidoborane-bis-η5-(2-"methy|-4-Pheny|inden-1 -yl)hafnium
dichloride;
bis(trimethylsilyl)amidoborane-bis-η5-(2-"methy|-4-Pheny|inden-1 -yl)hafnium
dimethyl;
bis(trimethylsilyl)amidoborane-bis-η5(2-"methy|-4-Pheny|inden-1 -yl)hafnium bis-dimethylamide;
bis(trimethylsilyl)amidoborane"bis-η5-((2-"methy|-4-Pheny|inden-1 -yl)hafnium
2-methyl-1 ,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5"(2-"methy|-4-Pheny|inden-1 -yl)hafnium
2,3-dimethyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5"(2-"methy|-4-Pheny|inden-1 -yl)hafnium
2-N,N-dimethylaminobenzyl;
bis(trimethylsilyl)amidoborane-bis--η5"(2-"methy|-4-Pheny|inden-1 -yl)hafnium
allyl;
bis(trimethylsilyl)amidoborane-bis--η5"(2-"methy|-4-Pheny|inden-1 -yl)hafnium
η4-1,4-diphenyl 1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5"(2-"methy|-4-Pheny|inden-1 -yl)hafniurn
η4-2,4-hexadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(2-"methy|-4-Pheny|inden-1 -yl)hafnium
η4 1,4-dinaphthyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5(2-"methy|-4-Pheny|inden-1 -yl)hafnium
η4-1 -phenyl-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-η5"(2-methyl-4-naphthylinden-1-yl)hafnium
η4-1.3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(2-"methy|-4-Pheny|inden-1 -yl)hafnium
dichloride;
bis(trimethylsilyl)amidoborane-bis-η5"(2-"methy|-4-Pheny|inden-1 -yl)hafnium dimethyl;

bis(trimethylsilyi)amidoborane-bis-η5-(3-isopropylinden-1 -yl)hafnium bis-dimethylamide;
bis(trimethylsilyl)amidoborane-bis-η5-(3-isopropylinden-1 -yl)haf nium 2-methyl-1,3-butadiene;
bis(trimethylsi!y!)amidoorare-bis-η5{3-isopropylinden-1-yl)hafnium2,3-dimethyM ,3-butadiene;
bis(trimethylsilyl)amidoborane-bis η5-(3-isopropylinden-1 -yl)hafnium 2-N.N-dimethylaminobenzyl;
bis(trimethylsilyl)amidoborane-bis-η5-(3-isopropylinden-1 -yl)hafnium allyl; bis(trimethylsilyl)amidoborane-bis-η5-(3-isopropylinden-1 -yl)hafnium η4-1,4-diphenyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-biS"η5-(3-isopropylinden-1-yl)hafniumη4-2,4-hexadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(3-isopropylinden-1 -yl)hafnium η4-1,4-dinaphthyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(3-isopropylinden-1 -yl)hafnium η4-1 -phenyl-1,3-pentadiene;
bis(trimethylsily})amidoborane"bis-η5-(3-,sopropytinden" 1 -yl)hafnium η4-1.3-pentadiene;
bis(trimethylsi!yl)amidoborane-bis-η5-(3-t-butylinden-1-yl)hafnium dichloride; bis(trimethylsilyl)amidoborane-bis-η5-(3-t-butylinden-1-y|)hafnium dimethyl;
bis(trimethylsilyl)amidoborane-bis-η5-(3-t-butylinden-1-y|)hafniumbis-dimethylamide;
bis(trimethylsilyl)amidoborane-bis-η5-(3-t-butylinden-1-y|)hafnium 2-methyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(3-t-butylinden-1-y|)hafnium2,3-dimethyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(3-t-butylinden-1-y|)hafnium2-N,N-dimethylaminobenzyl;
bis(trimethylsilyl)amidoborane-bisV-(3-t-butyhnden-1-yl)hafnium allyl;
bis(trimethylsilyl)amidoborane-bis-η5-(3-t-butylinden-1 -yl)hafnium η4-1,4-diphenyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(3.t-butylinden-1-yl)hafnium η4-2,4-hexadiene;

bis{trtrr\ethylsilyl)amidoborane-bis-"η5-{3-t"butylinden-1 -yl)hafnium η4-1,4-dinaphthyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(3-t-butylinden-1 -yl)hafnium η4-1 -phenyl-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-η5-(3-t-butylinden-1-yl)hafnium η4-1,3-pentadiene;
bis(dη5opropylamido)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1-yl)hafnium dichloride;
bis(dη5opropylamido)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1-yl)hafnium dimethyl;
bis(dη5opropylamido)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1-yl)hafnium bis-dimethylamide;
bis(dη5opropylamido)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1-yl)hafnium 2-methyl-1,3-butadiene;
bis(dη5opropylamido)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-l-yl)hafnium 2,3-dimethyl-1,3-butadiene;
bis(dη5opropylamido)diborane-1,2-bis-η5-(2-nnethy!-4-phenylinden-1-yl)hafnium2-N,N-dimethylaminobenzyl;
bis(dη5opropylamido)diborane-1,2-bis-η5-(2-methyl-4-phenyIinden-1 -yl)hafnium allyl;
bis(dη5opropylamido)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1-yl)hafnium η4-1 (4-dipheny!-1,3-butadiene;
bis(dη5opropylamido)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1-y!)hafnium η4-2,4-hexadiene;
bis(dη5opropylamido)diborane-1,2-bis-η5-(2-methyl"4-phenylinden-1-yl)hafnium η4-1,4-dinaphthyl-1,3-butadiene;
bis(dη5opropylamido)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1 -yl)hafnium Η4-1-phenyl-1,3-pentadiene;
bis(dη5opropylamido)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium Η4-1 ,3-pentadiene;
(η5-tetramethylcyclopentadienyl)(tert-butylamido)dη5opropylamidoborane titanium dichloride;

(η5-tetramethylcyclopentadienyl)(tert-η5-butylamido)dη5opropylamidoborane (i(anium dimethyl;
(η5-tetramethylcyclopentadienyl)(feη5-butylamido)dη5opropylamidoborane titanium bis-dimethylamide;
(η5-tetramethylcyclopentadieny!)(tert-butylamido)dη5opropylamidoborane titanium 2-methyl-1,3-butadiene;
(η5-tetramethylcyclopentadienyl)(tert-butylamido)dη5opropylamidoborane titanium 2,3-dimethyl-1,3-butadiene;
(η5-tetramethylcyclopentadienyl)(tert-butylamido)dη5opropylamidoborane titanium 2-N,N-dimethylaminobenzyl;
(η5-tetramethylcyclopentadienyl)(tert-butylamido)dη5opropylamidoborane titanium allyl;
(η5-tetramethylcyclopentadienyl)(tert"butylamido)dη5opropylamidoborane titanium η4-1,4-diphenyl-1,3-butadiene;
(η5-tetramethylcydopentadienyl)(fert-butylamido)dη5opropylamidoborane titanium η4-2.4-hexadiene;
(η5-tetramethylcyclopentadienyl)(tert-buty!amido)dη5opropylamidoborane titanium η4-l ,4-dinaphthyl-1,3-butadiene;
(η5-tetramethylcyclopentadienyl)(tert-butyiamido)dη5opropylamidoborane titanium η5"-1-phenyl-1,3-pentadiene;
(η5-tetramethylcyclopentadienyl)(tert-butylamido)dη5opropylamidoborane titanium η4-1.3-pentadiene;
(η5-tetramethylcyclopentadienyl)(cyclohexylamido)dη5opropylamidoborane titanium dichloride;
(η5-tetramethylcyclopentadienyl)(cyclohexylamido)dη5opropylamidoborane titanium dimethyl;
(η5-tetramethylcyclopentadienyl)(cyclohexylamido)dη5opropylamidoborane titanium bis-dimethylamide;
(η5-tetramethylcyclopentadienyl)(cyclohexylamido)dη5opropylamidoborane titanium 2-methyl-1,3-butadiene;
(η5-tetramethylcyclopentadienyl)(cyclohexylamido)dη5opropylamidoborane titanium 2,3-dimethyl-1,3-butadiene;

(η5-tetramethylcyclopentadienyl)(cyclohexylamido)dη5opropylamidoborane titanium 2-N.N-dimethylaminobenzyl;
(η5-tetramethylcyclopentadienyl)(cyclohexylamido)dη5opropylamidoborane titanium allyl;
(η5-tetrarnethylcyclopentadienyl)(cyclohexylamido)dη5opropylarmdob ane titanium η4-1 ,4-diphenyl-1,3-butadiene;
(η4-tetramethylcyclopentadienyl)(cyclohexylamido)dη5opropylamidoborane titanium η4-2,4-hexadiene;
(η5-tetramethylcyclopentadienyl)(cyclohexylamido)dη5opropylamidoborane titanium r}4-1,4-dinaphthyl-1,3-butadiene;
(η5-tetramethylcyclopentadienyl)(cyclohexylamido)dη5opropylamidoborane titanium η4-1 -phenyl-1,3-pentadiene;
(η5-tetramethylcyclopentadienyl)(cyclohexylamido)dη5opropylamidoborane titanium η4-1.3-pentadiene;
(η5-tetramethylcyclopentadienyl)(tert-butylamido) bis(dη5opropylamide) diborane titanium dichloride;
(η5-tetramethylcyclopentadienyl)(tert-butylamido) bis(dη5opropylamide) diborane titanium dimethyl;
(η5-tetramethylcyclopentadienyl)(tert-butylamido) bis(dη5opropylamide) diborane titanium bis-dimethylamide;
(η5-tetramethylcyclopentadienyl)(tert-butylamido) bis(dη5opropylamide) diborane titanium 2-methyl-1,3-butadiene;
(η5-tetramethylcyclopentadienyl)(tert-butylamido) bis(dη5opropylamide) diborane titanium 2,3-dimethyl-1,3-butadiene;
(η5-tetramethylcyclopentadienyl)(tert-butylamido) bis(dη5opropylamide) diborane titanium 2-N,N-dimethylaminobenzyl;
(η5-tetramethylcyclopentadienyl)(tert-butylamido) bis(dη5opropylamide) diborane titanium allyl;
(η5-tetramethylcyclopentadienyl)(tert-butylamido) bis(dη5opropylamide) diborane titanium η4-1,4-diphenyl-1,3-butadiene;
(η5-tetramethylcyclopentadienyl)(tert-butylamido) bis(dη5opropylamide) diborane titanium η4-2,4-hexadiene;

(η5-tetramethylcyclopentadienyl)(tert-butylamido) bis(dη5opropylamide) diborane titanium η4-1,4-dinaphthyl-1,3-butadiene;
(η5-tetramethylcyclopentadienyl)(tert-butylamido) bis(dη5opropylamide) diborane titanium η4~ 1 -phenyl-1,3-pentadiene;
(η5-tetramethylcyclopentadienyl)(tert-butylamido)bis(dη5opropylamide) diborane titanium η4-1,3-pentadiene;
(η5-tetramethylcyclopentadienyl)(phenylamido)dη5opropylamidoborane titanium dichloride;
(η5-tetramethylcyclopentadienyl)(phenylamido)dη5opropylamidoborane titanium dimethyl;
(η5-tetramethylcyclopentadienyl)(phenylamido)dη5opropylamidoborane titanium bis-dimethylamide;
(η5-tetramethylcyclopentadienyl)(phenylamido)dη5opropylamidoborane titanium 2-methyl-1,3-butadiene;
(η5-tetramethylcyclopentadienyl)(phenylamido)dη5opropylamidoborane titanium 2,3-dimethyl-1,3-butadiene;
(η5-tetramethylcyclopentadienyl)(phenylamido)dη5opropylamidoborane titanium 2-N,N-dimethylaminobenzyl;
(η5-tetramethylcyclopentadienyl)(phenylamido)dη5opropylamidoborane titanium allyl;
(η5-tetramethylcyclopentadienyl)(phenylamido)dη5opropylamidoborane titanium η4"-1,4-diphenyl-1,3-butadiene;
(η5-tetramethylcyclopentadienyl)(phenylamido)dη5opropylamidoborane titanium η4-2,4-hexadiene;
(η5-tetramethylcyclopentadienyl)(phenylamido)dη5opropylamidoborane titanium η4-1,4-dinaphthyl-1,3-butadiene;
(η5-tetramethylcyclopentadienyl)(phenylamido)dη5opropylamidoborane titanium η54-1 -phenyl-1,3-pentadiene;
(η5-tetramethylcyclopentadienyl)(phenylamido)dη5opropylamidoborane titanium η54-1,3-pentadiene;
(η5-tetramethylcyclopentadienyl)(tert-butylamido) dimethyiamidoborane titanium dichloride;

(η5-tetramethylcyclopentadienyl)(tertbutylamido) dimethylamidoborane titanium dimethyl;
(η5-tetramethylcyclopentadienyl)(tert-butylamido) dimethylamidoborane titanium bis-dimethylamide;
(η5-tetramethylcyclopentadienyljtert-butylamido) dimethylamidcborane titanium 2-metbyl-1,3-butadiene;
(n,3-tetramethylcyciopentadienyl)(tert-butylamido) dimethylamidoborane titanium 2,3-dimethyl-1,3-butadiene;
(η5-tetramethylcyclopentadienyl)(tet-butylamido) dimethylamidoborane titanium 2-N,N-dimethylaminobenzyl;
(η5-tetramethylcyclopentadienyl)(tert-butylamido) dimethylamidoborane titanium allyl;
(η5-tetramethylcyclopentadienyl)(tert-butylamido) dimethylamidoborane titanium η4-1,4-diphenyl-1,3-butadiene;
(η5-tetramethylcyclopentadienyl)(reη5-butylamido) dimethylamidoborane titanium η4-2,4-hexadiene;
(η5-tetramethylcyclopentadienyl)(rert-butylamido) dimethylamidoborane titanium η4-1,4-dinaphthyl-1,3-butadiene;
(η5-tetramethylcyclopentadienyl)(tert-butylamido) dimethylamidoborane titanium η4-1 -phenyI-1,3-pentadiene;
(η5-tetramethylcyclopentadienyl)(tert-butylamido) dimethylamidoborane titanium η4-1,3-pentadiene;
(η5-inden-1 -yl)(tert-butylamido)dissopropylamidoborane titanium dichloride;
(η5-inden-1 -yl)(fert-butylamido)dηiispropylamidoborane titanium dimethyl;
(η5-inden-1 -yl)(tert-butylamido)diisopropylamidoborane titanium bis-dimethylamide;
(η5-inden-1 -yl)(tert-butylamido)diisopropylamidoborane titanium 2-methyl-1,3-butadiene;
(η5-inden-l -yl)(tert-butylamido)diisopropylamidoborane titanium 2,3-dimethyl-1,3-butadiene;
(η5-inden-1 -yt)(tert-butylamido)diisopropylamidoborane titanium 2-N.N-dimethylaminobenzyl;
(η5-inden-1 -yl)(tert-butylamido)diisopropylamidoborane titanium allyl;

(η5-inden-1-yl)(tert-butylamido)dη5opropylamidoborane titanium η4-1,4-diphenyl-1,3-butadiene;
(η5-inden-1-yl)(tert-butylamido)dη5opropylamidoborane titanium η4-2,4-hexadiene;
(η5-inden-1-yl)(tert-butylamido)dη5opropylamidoborane titanium η4-1,4-dinaphthyl-1,3 butadiene;
(η5-inden-1-yl)(tert-butylamido)dη5opropylamidoborane titanium η4-1-phenyl-1,3-pentadiene;
(η5-inden-1-yl)(tert-butylamido)dη5opropylamidoborane titanium η4-1,3-pentadiene;
(η5-2,3-dimethyl-1-)(tert-butylamido)dη5opropylamidoborane titanium dichloride;
(η5-2,3-dimethylinden-1-yl)(tert-butylamido)dη5opropylamidoborane titanium dimethyl;
(η5-2,3-dimethylinden-1-yl)(tert-butylamido)dη5opropylamidoborane titanium bis-dimethylamide;
(η5-2,3-dimethylinden-1 -yl)(tert-butylamido)dη5opropylamidoborane titanium 2-methyl-1,3-butadiene;
(η5-2,3-dimethylinden-1-yl)(tert-butylamido)dη5opropylamidoborane titanium 2,3-dimethyl-1,3-butadiene;
(η5-2,3-dimethylinden-1 -yl)(tert-butylamido)dη5opropylamidoborane titanium 2-N.N-dimethylaminobenzyl;
(η5-2,3-dimethylinden-1-yl)(tert-butylamido)dη5opropylamidoborane titanium aliyl;
(n5-2.3-dimethylinden-1-yl)(tert-butylamido)dη5opropylamidoborane titanium Η4-1 ,4-diphenyl-1,3-butadiene;
(η5-2,3-dimethylinden-1-yl)(tert-butylamido)dη5opropylamidoborane titanium η4-2.4-hexadiene;
(η5-2,3-dimethylinden-1-yl)(tert-butylamido)dη5opropylamidoborane titanium η4-1,4-dinaphthyl-1,3-butadiene;
(η5-2,3-dimethylinden-1-yl)(tert-butylamido)dη5opropylamidoborane titanium Η4- 1 -phenyl-1,3-pentadiene;

(η5-2,3-dimethylinden-1-yl)(tert-butylamido)dη5opropylamidoborane titanium η4-1,3-pentadiene;
(η5-2-pyrrolidenylinden-1-yl)(tert-butylamido)dη5opropylamidoborane titanium dichloride;
(η5-2-py roiidenylinden-1-yl)(tert-butyiamido)dη5opropylamidc" orane : iium dimethyl;
(η5-2-pyrrolidenylinden-1-yl)(tert-butylamido)dη5opropylamidoborane titanium bis-dimethylamide;
(η5-2-pyrrolidenylinden-1 -yl)(tert-buty!amido)dη5opropylamidoborane titanium 2-methyl-1,3-butadiene;
(η5-2-pyrrolidenylinden-1-yl)(tert-butylamido)dη5opropylamidoborane titanium 2,3-dimethyl-1,3-butadiene;
(η5-2-pyrrolidenylinden-1-yl)(tert-butylamido)dη5opropylamidoborane titanium 2-N,N-dimethylaminobenzyl;
(η5-2-pyrrolidenylinden-1-yl)(tert-butylamido)dη5opropylamidoborane titanium allyl;
(η5-2-pyrrolidenylinden-1-yl)(tert-butylamido)dη5opropylamidoborane titanium η4-1,4-diphenyl-1,3-butadiene;
(η5-2-pyrrolidenylinden-1-yl)(tert-butylamido)dη5opropylamidoborane titanium η4-2,4-hexadiene;
(η5-2-pyrrolidenylinden-1-yl)(tert-butylamido)dη5opropylamidoborane titanium η4-1,4-dinaphthyl-1,3-butadiene;
(η5-2-pyrrolidenylinden-1-yl)(tert5-butylamido)dη5opropylamidoborane titanium η54-1-phenyl-1,3-pentadiene;
(η5-2-pyrrolidenylinden-1-yl)(tert-butylamido)dη5opropylamidoborane titanium η4-1,3-pentadiene:
bis-pheny1amido-bis(diisopropylamido)diborane titanium dichloride;
bis-phenylamidb-bis(diisopropylamido)diborane titanium dimethyl;
bis-phenylamido-bis(diisopfopylamido)diborane titanium bis-dimethylamide;
bis-phenylamido-bis(diisopropylamido)diborane titanium 2-methyl-1,3-butadiene;
bis-phenylamido-bis(diisopropylamido)diborane titanium 2,3-dimethyl-1,3-butadiene;

bis-phenylamido-bis(dη5opropylamido)diborane titanium 2-N.N-dimethylaminobenzyl;
bis-phenylamido-bis(diisopropylamido)diborane titanium allyl;
bis-phenylamido-bis(diisopropylamido)diborane titanium η54-1,4-diphenyl-1,3-butadiene;
bis-phenylamido-bis(diisopropylamido)diborane titanium η4-2,4-hexadiene;
bis-phenylamido-bis(diisopropylamido)diborane titanium η4-1,4-dinaphthyl-1,3-butadiene;
bis-phenylamido-bis(diisopropylamido)diborane titanium η4-1 -phenyl-1,3-pentadiene;
bis-phenylamido-bis(diisopropylamido)diborane titanium Η4-1 ,3-pentadiene;
bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diborane titanium dichloride;
bis-2,6-diisopropylphenylamido-bis(diisopropylamido)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 η4-2,4-hexadiene;
bis-2.6-diisopropylphenylamido-bis(diisopropylamido)diborane titanium η4-1,4-dinaphthyl-1,3-butadiene;
bis-2,6-diiisopropylphenylamido-bis(diisopropylamido)diborane titanium η4-1-phenyl-1,3-pentadiene;
bis-2,6-dη5opropylphenylamido-bis(diisopropylamido)diborane titanium Η4-1 ,3-pentadiene;

bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titanium dichloride
bis-3,5-dimethylbenzylamido-bis(dirnethylamido)diborane titanium dimethyl;
bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titanium bis-dim c thy! amide;
bis-3,5-dimethylbenzylamido-bis(dimemylamido)d(borane titanium 2-methyl-1,3-butadiene;
bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titanium 2,3-dimethyl-1,3-butadiene;
bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titanium 2-N.N-dimethylaminobenzyl;
bis-3,5~dimethylbenzylamido-bis(dimethylamido)diborane titanium allyl,
bis-3,5--dimethyIbenzylamido-bis(dimethylamido)diborane titanium Η4-1 ,4-diphenyl-1,3-butadiene;
bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titanium η4-2,4-hexadiene;
bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titanium η4-1,4-dinaphthyl-1,3-butadiene;
bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titanium η4-1 -phenyl-1,3-pentadiene;
bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titanium η4-1,3-pentadiene;
bis-2,6-dimethylbenzylamido-bis(dimethy)amido)diborane titanium dichloride
bis-2,6-dimethylbenzylamido-bis(dimethylamido)diborane titanium dimethyl;
bis-2,6-dimethylbenzylamido-bis(dimethylamido)diborane titanium bis-dimethyiamide;
bis-2,6-dimethylbenzylamido-bis(dimethylamido)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-dimethyiaminobenzyl;
bis-2,6-dimethylbenzylamido-bis(dimethylamido)diborane titanium ally!;

bis-2,6-dimethylbenzylamido-bis(dimethylamido)diborane titanium Η4-1 ,4-diphenyl-1,3-butadiene;
bis-2,6-dimethylbenzylamido-bis(dimethylamido)diborane titanium η4-2,4-hexadiene;
bis-2,6-dimethylbenzylamido-bis(dimethylamido)diborane titanium η4-1,4-dinaphthyl-1,3-butadiene;
bis-2,6-dimethylbenzylamido-bis(dimethylamido)diborane titanium Η4-1 -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 η4-1,4-diphenyl-1,3-butadiene;
bis-2,6-diisopropylphenylamido-bis(dimethylamido)diborane titanium η4-2,4-hexadiene;
bis-2,6-diisopropylphenylamido-bis(dimethylamido)diborane titanium η4-1,4-dinaphthyl-1,3-butadiene;
bis-2,6-diisopropylphenylamido-bis(dimethylamido)diborane titanium Η4-1 -phenyl-1,3-pentadiene;
bis-2,6-diisopropylphenylamido-bis(dimethylamido)diborane titanium η4-1,3-pentadiene;

bis-2,6-diisopropylphenylamido-bis(bis(trimethylsilyl)amido)diborane titanium dichloride;
bis-2.6-diisopropylphenylamido-bis(bis(trimethylsilyl)amido)diborane titanium dimethyl;
bis-2?6-diisopropylphenylamido-bis(bis(tnmethylsilyi)amido)diborane tifinium bis-dimethylamide;
bis-2,6-diisopropylphenylamido-b:3(bis(trimethylsily!)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-diisopropylphenylamido-bis(bis(trimethylsilyl)amido)diborane titanium η4-1,4-diphenyl-1,3-butadiene;
bis-2,6-diisopropylphenyfamido-bis(bis(trimethylsilyl)amido)diborane titanium η4-2,4-hexadiene;
bis-2,6-diisopropylphenylamido-bis(bis(trimethylsilyl)amido)diborane titanium η4-1,4-dinaphthyl-1,3-butadiene;
bis-2,6-diisopropylphenylamido-bis(bis(trimethylsilyl)amido)diborane titanium η4-1 -phenyl-1,3-pentadiene;
bis-2,6-diisopropylphenyiamido-bis(bis(trimethylsilyl)amido)diborane titanium η4-1,3-pentadiene;
bis-2,6-diisopropylphenylamido-bis(dη5opropylamido)diborane zirconium dichloride;
bis-2,6-diisopropylphenylamido-bis(dη5opropylamido)diborane zirconium dimethyl;
bis-2,6-diisopropylphenylamido-bis(dη5opropylamido)diborane zirconium bis-dimethylamide;
bis-2,6-diisopropylphenylamido-bis(dη5opropylamido)diborane zirconium 2-methyl-1,3-butadiene;
bis-2,6-diisopropylphenylamido-bis(dη5opropylamido)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 Η4-1,4-diphenyl-1,3-butadiene;
bis-2>6-diisopropylphenylamido-bis(diisopropylamido)diborane zirconium Η4-2,4-hexadiene;
bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diborane zirconium η4-1,4-dinaphthyl-1,3-butadiene;
bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diborane zirconium η4-l -phenyl-1,3-pentadiene;
bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diborane zirconium η4-1,3-pentadiene;bis-2-tert-butylphenylamido~bis(diisopropylamido)diborane titanium dichloride;
bis-2-tert-butylphenylamido-bis(diisopropylamido)diborane titanium dimethyl;
bis-2-tert-butylphenylamido-bis(diisopropylamido)diborane titanium bis-dimethylamide;
bis-2-tert-butylphenylamido-bis(diisopropylamido)diborane titanium 2-methyl-• 1,3-butadiene;
bis-2-tert-butylphenylamido-bis(diisopropylamido)diborane titanium 2,3-dimethyl-1,3-butadiene;
bis-2-tert-butylphenylamido-bis(diisopropylamido)diborane titanium 2-N.N-dimethylaminobenzyl;
bis-2-tert-butylphenylamido-bis(diisopropylamido)diborane titanium allyl;
bis-2-tert-butylphenylamido-bis(diisopropylamido)diborane titanium η4-1.4-diphenyl-1,3-butadiene;
bis-2-tert-butylphenylamido-bis(diisopropylamido)diborane titanium Η4-2,4-hexadiene;
bis-2-tert-butylphenylamido-bis(diisopropylamido)diborane titanium η4-1,4-dinaphthyl-1,3-butadiene;
bis-2-tert-butylphenylamido-bis(diisopropylamido)diborane titanium η4-1 -phenyl-1,3-pentadiene; and
bis-2-tert-butylphenylamido-bis(diisopropylamido)diborane titanium η4-1,3-pentadiene.

A further preferred class of Group 4 transition metal complexes of the present invention are represented in previously defined formulas 4-9 wherein T is :

including such structures where two R1 groups and Rs are linked such as in 1,3.4.6,7,8, hexahydro-pyrimido[1,2-a] pyrimidinate, shown below:

In the foregoing species, it is believed, without wishing to be bound by such belief, that the ligand group, T, is connected to Z via the heteroatoms thereof.
Specific, but not limiting, examples of the foregoing metal complexes included within the invention are:
N,N"-diisopropyl-phenyl-amidinateborane-bis-η5-cyclopentadienylzirconium dichloride;
N,N"-diisopropyl-phenyl-amidinateborane-bis-η5-cyclopentadienylzirconium dimethyl;
N,N"-diisopropyl-phenyl-amidinate borane-bis-η5-cyclopentadienylzirconium bis-dimethylamide;
N,N -diisopropyl-phenyl-amidinate borane-bis-η5-cyclopentadienylzirconium 2-methyl-1,3-butadiene;
N.N"-diisopropyl-phenyl-amidinate borane-bis-η5-cyclopentadienylzirconium 2,3-dimethyM ,3-butadiene;
N,N -diisopropyl-phenyl-amidinate borane-bis-η5-cyclopentadienylzirconium 2-N(N-dimethylaminobenzyl;
N,N"-diisopropyl-phenyl-amidinate borane-bis-η5-cyclopentadienyl zirconium ally I;
N,N"-diisopropyl-phenyl-amidinate borane-bis--η5-cyclopentadienylzirconium η4-1 ,4-diphenyl-1,3-butadiene;
N.N"-diisopropyl-phenyl-amidinate borane-bis-η5-cyclopentadienylzirconium η4-2,4-hexadiene;

N.N"-dη5opropyl-phenyl-amidinate borane-bis-η5-cyclopentadienylzirconium η4-1,4-dinaphthyl-1,3-butadiene;
N,N"-dη5opropyl-phenyl-amidinate borane-bis-η5-cyclopentadienylzirconium η4-1 -phenyl-1,3-pentadiene;
N.N"-dη5opropyl-phenyl-amidinate borane-bis-η5-cyclopentadienylzirconium η4-1,3-pentadiene;
N,N -dη5opropyl-3-phenyl-1,3-diketimine borane-bis-η5-cyclopentadienylzirconium dichloride;
N,N"-dη5opropyl-3-phenyl-1,3-diketimine borane-bis-η5-cyclopentadienylzirconium dimethyl;
N,N"-dη5opropyl-3-phenyl-1,3-diketimine borane-bis-η5-cyclopentadienylzirconium bis-dimethylamide;
N,N"-dη5opropyl-3-phenyl-1,3-diketimine borane-bis-η5-cyclopentadienylzirconium 2-methyl-1,3-butadiene;
N,N"-dη5opropyl-3-phenyl-1,3-diketimine borane-bis-V-cyclopentadienylzirconium 2,3-dimethy 1 ,3-butadiene;
N,N"-dη5opropyl-3-phenyl-1,3-diketimine borane-bis-η5-cyclopentadienylzirconium 2-N.N-dimethylaminobenzyl;
N,N"-dη5opropyl-3-phenyl-1,3-diketimine borane-bis-η5-cyclopentadienylzirconium allyl;
N,N"-dη5opropyl-3-phenyl-1,3-diketimine borane-bis-η5-cyclopentadienylzirconium Η4-1 ,4-diphenyl-1,3-butadiene;
N,N"-dη5opropyl-3-phenyl-1,3-diketimine borane-bis-η5-cyclopentadienylzirconium η4-2,4-hexadiene;
N,N -dη5opropyl-3-phenyl-1,3-diketimine borane-bis-η5-cyclopentadienylzirconium η4-1,4-dinaphthyl-1,3-butadiene;
N,N"-dη5opropyl-3-phenyl-1,3-diketimine borane-bis-η5-cyclopentadienylzirconium η4-1 -phenyl-1,3-pentadiene;
N,N"-dη5opropyl-3-phenyl-1,3-diketimine borane-bis-η5-cyclopentadienylzirconium η4-1 ,3-pentadiene;
N,N"-dη5opropyl-dimethylguanidinate borane-bis-η5-cyclopentadienylzirconium dichloride;

N.N"-diisopropyl-dimethylguanidinate borane-bis-η5-cyclopentadienylzirconium dimethyl;
N.N"-diisopropyl-dimethylguanidinate borane-bis~η5-cyclopentadienylzirconium bis-dimethylamide;
N.N"-diisopropyl-dimethyiguanidinate borane-bis-η5-cyclopentadienylzirconium 2-methyl-1,3-butadiene;
N,N-diisopropyl-dimethylguanidinate borane-bis-η5-cyclopentadienylzirconium 2,3-dimethyl-1,3-butadiene;
N.N"-diisopropyl-dimethylguanidinate borane-bis-η5-cyclopentadienylzirconium 2-N,N-dimethylaminobenzyl;
N.N"-diisopropyl-dimethylguanidinate borane-bis-η5-cyclopentadienylzirconium allyl;
N,N"-diisopropyl-dimethylguanidinate borane-bis-η5-cyclopentadienylzirconium η4-1,4-diphenyl-1,3-butadiene;
N,N"-diisopropyl-dimethylguanidinate borane-bis-η5-cyclopentadienylzirconium η4-2,4-hexadiene;
N.N"-diisopropyl-dimethylguanidinate borane-bis-η5-cyclopentadienylzirconium η4-1,4-dinaphthyl-1,3-butadiefte;
N.N"-diisopropyl-dimethylguanidinate borane-bis-η5-cyclopentadienylzirconium Η4-1 -phenyl-1,3-pentadiene;
N.N"-diisopropyl-dimethylguanidinate borane-bis-η5-cyclopentadienylzirconium η4-1,3-pentadiene;
1,3,4,6,7,8-hexahydro-pyrimidotl ,2-a) pyrimidinate borane-bis-η5-inden-1 -ylzirconium dichloride;
1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinate borane-bis-η5-inden-1 -ylzirconium dimethyl;
1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinate borane-bis-η5-inden-1 -ylzirconium bis-dimethylamide;
1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinate borane-bis-η5-inden-1 -ylzirconium 2-methy 1 ,3-butadiene;
1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinate borane-bis-η5-inden-1 -ylzirconium 2,3-dimethy!-l ,3-butadiene;

1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinate borane-bis-η5-inden-1-ylzirconium 2-N,N-dimethyiaminobenzyl;
1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinate borane-bis-η5-inden-1-ylzirconium allyl;
1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinate borane-bis-η5-inden-1-ylzirconium η4-1,4-diphenyl-1,3-butadiene;
1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinate borane-bis-η5-inden-1 -ylzirconium η4-2,4-hexadiene;
1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinate borane-bis-η5-inden-1-ylzirconium η4-1 ,4-dinaphthyl-1,3-butadiene;
1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinate borane-bis-η5-inden-1-ylzirconium η4-1-phenyl-1,3-pentadiene;
1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinate borane-bis-η5-inden-1 -ylzirconium Η4-1 ,3-pentadiene;
N,N"-diisopropyl-phenyl-amidinate borane-bis-η5-(2-methylinden-1-yl)zirconium dichloride;
N,N "-diisopropyl-phenyl-amidinate borane-bis-η5-(2-methylinden-1 -yl)zirconium dimethyl;
N,N"-diisopropyl-phenyl-amidinate borane-bis-η5-(2-methylinden-1-yl)zirconium bis-dimethylamide;
N.N-diisopropyl-phenyl-amidinate borane-bis-η5-(2-methylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
N.N-diisopropyl-phenyl-amidinate borane-bis-η5-(2-methy!inden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
N.N"-diisopropyl-phenyl-amidinate borane-bis-η5-{2-methylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
N.N -diisopropyl-phenyl-amidinate borane-bis-η5-(2-methylinden-1 -yl)zirconium allyl;
N,N-diisopropyl-phenyl-amidinate borane-bis-η5-(2-methylinden-1-yl)zirconium η4-1,4-diphenyl-1,3-butadiene;
N.N -diisopropyl-phenyl-amidinate borane-bis-η5-(2-methylinden-1-yl)zirconium rt4-2,4-hexadiene;

N.N -diisopropyl-phenyl-amidinate borane-bis-η5 -(2-methylinden-1 -yl)zirconium Η4-1 ,4-dinaphthyl-1,3-butadiene;
N,N-diisopropyl-phenyl-amidinate borane-bis-η5-(2-methylinden-1-yl)2irconium Η4-1 -phenyl-1,3-pentadiene;
N.N"-diisopropyl-phenyl-amidinate borane-bis-η5-(2-methylinden-1-yl)zirconium η4-1,3-pentadiene;
N,N"-bis-2,6-diisopropylphenyl-phenyl-amidinate borane-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium dichloride;
N,N"-bis-2,6-diisopropylphenyl-phenyl-amidinateborane-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium dimethyl;
N,N"-bis-2,6-diisopropylphenyl-phenyl-amidinateborane-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium bis-dimethylamide;
N,N"-bis-2,6-diisopropylphenyl-phenyl-amidinate borane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
N,N"-bis-2,6-diisopropylphenyl-phenyl-amidinateborane-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium 2,3-dimethyl-1,3-butadiene;
N,N"-bis-2,6-diisopropylphenyl-phenyl-amidinate borane-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium 2-N,N-dimethylaminobenzyl;
N1N"-bis-2,6-diisopropylphenyl-phenyl-amidinateborane-bis-η5*(2-methyl-4-phenylinden-1 -yl)zirconium allyl;
N,N"-bis-2,6-diisopropylphenyl-phenyl-amidinate borane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium η4-1,4-diphenyl-1,3-butadiene;
N,N"-bis-2,6-diisopropylphenyl-phenyl-amidinate borane-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium η4-2,4-hexadiene;
N,N"-bis-2,6-diisopropylpheny(-phenyl-amidinate borane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium η4-1 ,4-dinaphthyl-1,3-butadiene;
N,N"-bis-2,6-diisopropylphenyl-phenyl-amidinate borane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium η4-1-phenyl-1,3-pentadiene;
N,N"-bis-2,6-diisopropylphenyl-phenyl-amidinateborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium η4-1,3-pentadiene;
N,N"-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium dichloride;

N,N"-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimineborane-bis-η5-(2-rnethyl-4-phenylinder>1-yl)zirconium dimethyl;
N,N"-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium bis-dimethylamide;
N,N -bis-2,6-diisopropylphenyl-3-methyl-1 ,3-diketimine borane-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium 2-methyl-1,3-butadiene;
N,N"-bis-2.6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium 2,3-dimethyl-1,3-butadiene;
N,N"-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimineborane-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium 2-N,N-dimethylaminobenzyl;
N,N -bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium allyl;
N,N"-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium Η4-1 ,4-diphenyM,3-butadiene;
N,N"-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimineborane-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium η4-2,4-hexadiene;
N,N "-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium Η4-1 ,4-dinaphthyl-1,3-butadiene;
N,N"-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium η4-1 -phenyl-1,3-pentadiene;
N,N"-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimineborane-bis-iis-(2-methyl-4-phenylinden-1-yl)zirconium η4-1,3-pentadiene;
bis(N,N"-diisopropyl-phenyl-amidinate)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium dichloride;
bis(N,N"-dttsopropyl-phenyt-amidina\e)dborane-1,2-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium dimethyl;
bis(N,N -diisopropyl-phenyl-amidinate)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium bis-dimethylamide;
bis(N,N"-diisopropyl-phenyl-amidinate)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
bis(N ,N -diisopropyl-pheayl-amidinate)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium 2,3-dimethyl-1,3-butadiene;

bis(N,N"-diisopropyl-phenyl-amidinate)diborane-1,2-bis-η5-{2-methy{-4-phenylinden-1 -yl)zirconium 2-N,N-dimethylaminobenzyl;
bis(N,N"-diisopropyl-phenyl-amidinate)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium allyl;
bis(N,N"-diisopropyl-phenyl-amidinate)diborane-1,2-bis-η5-(2"methyl-4-phenyiinden-1 -yl)zirconium η4-1,4-diphenyl-1,3-butadiene;
bis(N,N"-diisopropyl-phenyl-amidinate)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium η4-2,4-hexadiene;
bis(N,N"-diisopropyl-phenyl-amidinate)diborane-1.2-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium η4-1,4-dinaphthyl-1,3-butadiene;
bis(N,N"-diisopropyl-phenyl-amidinate)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium Η4-1-phenyl-1,3-pentadiene;
bis(N,N"-diisopropy-phenyl-amidinate)diborane-1,2-bis-η5-(2-methy)-4-phenylinden-1-yl)zirconium Η4-1 ,3-pentadiene;
bis(N,N"-diisopropyl-3-phenyl-1,3-diketimine)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium dichloride;
bis(N,N"-diisopropyl-3-pheny!-1,3-diketimine)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium dimethyl;
bis(N,N"-diisopropyl-3-phenyl-1,3-diketimine)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium bis-dimethylamide;
bis(N,N"-diisopropyl-3*phenyl-1,3-diketimine)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
bis(N,N"-diisopropyl-3-phenyl-1,3-diketimine)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
bis(N,N"-diisopropyl-3-phenyl-1,3-diketimine)diborane-1l2-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium 2-N,N-dimethylaminobenzyl;
bis(N,N"-diisopropyl-3-phenyl-1,3-diketimine)diborane-1,2-bis-η5-{2-methyl-4-phenylinden-1 -yl)zirconium allyl;
bis(N,N"-diisopropyl-3-phenyl-1.3-diketimine)diborane-1,2-bis-η5-(2-nnethyl-4-phenylinden-1-yl)zirconium n/-1,4-diphenyl-1,3-butadiene;
bis(N,N"-diisopropyl-3-phenyl-1,3-diketimine)diborane-1I2-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium η4-2,4-hexadiene;

bis(N,N -diisopropyl-3-phenyt-1,3-diketimine)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium η4-1,4-dinaphthyl-1,3-butadiene;
bis(N,N"-diisopropyl-3-phenyl-1,3-diketimine)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium η4-1-phenyl-1,3-pentadiene;
bis(N,N"-diisopropyl-3-phenyl-1,3-diketimine)diborane-1,2-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium η4-1,3-pentadiene;

N.N"-diisopropyl-phenyl-amidinate borane-bis-η5 yl)zirconium dichloride;
N,N -diisopropyl-phenyl-amidinate borane-bis-η5 -yl)zirconium dimethyl;
N,N -diisopropyl-phenyl-amidinate borane-bis-η5 -yl)zirconium bis-dimethylamide;
N,N -diisopropyl-phenyl-amidinate borane-bis-η5 -yl)zirconium 2-methyl-1,3-butadiene;
N,N"-diisopropyl-phenyl-amidinate borane-bis-η5 -yl)zirconium 2,3-dimethyl-1,3-butadiene;
N,N"-diisopropyl-phenyl-amidinate borane-bis-η5 -yl)zirconium 2-N,N-dimethylaminobenzyl;
N,N"-diisopropyl-phenyl-amidinate borane-bis-η5--yl)zirconium allyl;
N,N-diisopropyl-phenyl-amidinate borane-bts-η5--yl)zirconium Η4-1 ,4-diphenyl-1,3-butadiene;
N,NT-diisopropyl-phenyl-amidinate borane-bis-η5--yl)zirconium iis4-2,4-hexadiene;
N,N-diisopropyl-phenyl-amidinate borane-bis-η5--yl)zirconium n"-1,4-dinaphthyl-1,3-butadiene;
N,N-diisopropyl-phenyl-amidinate borane-bis-η5--yl)zirconium η4-1 -phenyl-1,3-pentadiene;
N.N"-diisopropyl-phenyl-amidinate borane-bis-η5--yl)zirconium iis4-1,3-pentadiene;

2-methyl-4-naphthy)inden-l -
2-methyl-4- naphthylinden-
2-methyl-4- naphthylinden-
2-methyl-4- naphthylinden-
2-methyl-4- naphthylinden-
2-methyl-4- naphthylinden-
2-methyl-4- naphthylinden-
2-methyl-4- naphthylinden-
2-methyl-4- naphthylinden-
2-methyl-4- naphthylinden-
2-methyl-4- naphthylinden-
2-methyl-4- naphthylinden-

N,N"-diisopropyl-3-phenyl-1,3-diketimine borane-bis-η5-(2-methyl-4-naphthylinden-1 -yl)zirconium dichloride;

N,N"-diisopropyl-3-phenyl-1,3-diketimine borane-bis-η5-(2-methyl-4-naphthylinden-l-yl)zirconium dimethyl;
N,N -diisopropyl-3-phenyl-1,3-diketimine borane-bis-η5-(2-methyl-4-naphthylinden-1 -yl)zirconium bis-dimethylamide;
N,N"-(.cusopropyl-3-phenyl-1,3-diketimine borane-bis-η5-methyl-naphthylinden-1 -yl)zirconium 2-methyl-1,3-butadiene;
N,N"-diisopropyl-3-phenyl-1,3-diketimineborane-bis-η5-(2-methyl-4-naphthylinden-1 -yl)zirconium 2,3-dimethyl-1,3-butadiene;
N,N"-diisopropyl-3-phenyl-1,3-diketimineborane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
N,N -diisopropyl-3-phenyl-1,3-diketimine borane-bis-η5-(2-methyl-4-naphthylinden-1 -yl) zirconium allyl;
N,N -diisopropyl-3-phenyl-1,3-diketimine borane-bis-η5-(2-methyl-4-naphthylinden-1-yl)zirconium η4-1,4-diphenyl-1,3-butadiene;
N.N -diisopropyl-3-phenyl-1,3-diketimine borane-bis-η5-(2-methyl-4-naphthylinden-1 -yl)zirconium η4-2,4-hexadiene;
N,N"-diisopropyl-3-pheny1,3-diketimineborane-bis-η5-(2-methyl-4-naphthylinden-1 -yl)zirconium η4-1,4-dinaphthyl-1,3-butadiene;
N,N -diisopropyl-3-phenyl-1,3-diketimine borane-bis-η5-(2-methyl-4-naphthyfinden-1-yl)zirconium η4-1-phenyl-1,3-pentadiene;
N.N -diisopropyl-3-phenyl-1,3-diketimine borane-bis-η5-(2-methyl-4-naphthylinden-1 -yl)zirconium η54-1,3-pentadiene;
bis-2,6-diisopropylphenylamidd-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)diborane titanium bis-dimethylamide;
bis-2,6-diisopropylphenylamido-bis(N,N"-diisopropyl-phenyl-amidinate)diborane titanium 2-methyl-1,3-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"-diisopropyl-phenyl-amidinate)diborane titanium 2-N,N-dimethylaminobenzyl;

bis-2,6-diisopropylphenylamido-bis(N,N"-diisopropyl-phenyl-amidinate)dtborane titanium allyl;
bis-2,6-diisopropylphenylamido-bis(N,N"-diisopropyl-phenyl-amidinate)diborane titanium η54-1,4-diphenyl-1,3-butadiene;
bis-2,6-diisopropylphenylamido-bis(N,N"-diisopropyl-phenyl-amidinate)diborane titanium η4-2.4-hexadiene;
bis-2,6-diisopropylphenylamido-bis(N,N"-diisopropyl-phenyl-amidinate)diborane titanium η4-1,4-dinaphthyM,3-butadiene;
bis-2,6-diisopropylphenylamido-bis(N,N"-diisopropyl-phenyl-amidinate)diborane titanium η54-1-phenyl-1,3-pentadiene;
bis-2,6-diisopropylphenylamido-bis(N,N""diisopropyl-phenyl-amidinate)diborane titanium η4-1,3-pentadiene;
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-phenyl-1,3-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 2-N,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 η4-1,4-diphenyl-1,3-butadiene;
bis-2,6-diisopropylphenylamido-bis(N,N"-diisopropyl-3-phenyl-1,3-diketimine)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-1.3-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-I.3-pentadiene.
The skilled ariisan will recognize that additional members of the foregoing list, such as those wherein boron is replaced by aluminum are also included within the invention. Moreover, it should also be recognized that tne terms η5 or η4 may not accurately reflect the actual electronic distribution of the molecule under use conditios, and that molecules including lesser numbers of contributing atoms to the electronic delocation are intended to be included within such descriptioη5 as well.
The most highly preferred metal complexes for use herein are: dimethylamidoborane-bis(η5-cyclopentadienyl)zirconium dichloride, dimethylamidoboranebis(η5-inden-1 -yl)zirconium dichloride, dimethylamidoborane-bis(η5-2-methyl-4-phenylinden-1 -yl)zirconium dichloride, dimethylamidoborane-bis(η5-2-ethyl-4-phenylinden-1 -yl)zirconium dichloride, dimethylamidoborane-bis(η5-2-isopropyl-4-phenylinden-1 -yl)zirconium dichloride, dimethylamidoborane-bis(η5-2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium dichloride, dimethylamidoborane-bis(η5-3-t-butylinden-1-yl)zirconium dichloride,
dη5opropylamidoborane-bis(η5-cyclopentadienyl)zirconium dichloride, dη5opropylamidoboranebis(η5-inden-1 -yl)zirconium dichloride, dη5opropylamidoborane-bis(η5-2-methyl-4-phenylinden-1-yl)zirconium dichloride, dη5opropylamidoborane-bis(η5-2-ethyl-4-phenylinden-1-yl)zirconium dichloride, dη5opropylamidoborane-bis(η5-2-isopropy1-4-phenylinden-1-yl)zirconium dichloride, dη5opropylamidoborane-bis(η5-2-methyl-4-bis(3.5-trifluoromethyl)phenylinden-1-yl)zirconium dichloride, dη5opropylamidoborane-bis(η5-3-t-butylinden-1 -yl)zirconium dichloride,
diphenylamidoborane-bis(η5-cyclopentadienyl)zirconium dichloride, diphenyiamidoboranebis(η5-inden-1 -yl)zirconium dichloride, diphenylamidoborane-bis(η5-2-methyl-4-phenylinden-1 -yl)zirconium dichloride, diphenylamidoborane-bis(η5-2-ethyl-4-phenylinden-1 -yl)zirconium dichloride, diphenylamidoborane-bis(η5-2-isopropyl-4-phenylinden-1 -yl)zirconium dichloride, diphenylamidoborane-bis(η5-2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium dichloride, diphenylamidoborane-bis(η5-3-t-butylinden-1-yl)zirconium dichloride,
dimethylamidoborane-bis(η5-cyclopentadienyl)zirconium 1,4-diphenyl-1,3-butadiene, dimethylamidoboranebis(η5-inden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, dimethylamidoborane-bis(η5-2-methyl-4-phenylinden-1 -yl)zirconium 1,4-

diphenyl-1,3-butadiene, dimethylamidoborane-bis(η5-2-ethyl-4-phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, dimethylamidoborane-bis(η5-2-isopropyl-4-phenylinden-1 -yl)zirconium 1,4-diphenyl-1,3-butadiene, dimethylamidoborane-bis(η5-2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1 -yl)zirconium 1,4-diphenyl-1,3-butadiene, dimethylamidoborane-bis(η5-3-t-butylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene,
dη5opropylamidoborane-bis(η5-cyclopentadienyl)zirconium 1,4-diphenyl-1,3-butadiene, dη5opropylamidoboranebis(η5-inden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, dη5opropylamidoborane-bis(η5-2-methyl-4-phenylinden-1-yl)zirconium 1.4-diphenyl-1,3-butadiene, dη5opropylamidoborane-bis(η5-2-ethyl-4-phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, dη5opropylamidoborane-bis(η5-2-isopropyl-4-phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, dη5opropylamidoborane-bis(η5-2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1 -yl)zirconium 1,4-diphenyl-1,3-butadiene, dη5opropy!amidoborane-bis(η5-3-t-butylinden-1 -yl)zirconium 1,4-diphenyl-1,3-butadiene,
diphenylamidoborane-bis(η5-cyclopentadienyl)zirconium 1,4-diphenyl-1,3-butadiene, diphenylamidoboranebis(η5-inden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, diphenylamidoborane-bis(η5-2-methyl-4-phenylinden-1 -yl)zirconium 1,4-diphenyl-1,3-butadiene, diphenylamidoborane-bis(η5-2-ethyl-4-phenylinden-1 -yl)zirconium 1,4-diphenyl-1,3-butadiene, diphenylamidoborane-bis(η5-2-isopropyl-4-phenylinden-1 -yl)zirconium 1,4-diphenyl-1,3-butadiene, diphenylamidoborane-bis(η5-2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, or diphenylamidoborane-bis(η5-3-t-butylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene.
In general the complexes of the current invention can be prepared by first converting the ligands represented in formulas 1a and 2a to a dianionic salt (where R4 is H) via reaction with an alkyl lithium, Grignard reagent, or alkali metal hydride such as NaH or KH. The dianionic ligand derivative is then reacted with a metal complex precursor such as MY34, MY33. or MY32 (and the corresponding Lewis base adducts), where Y3 is defined as above. Alternatively, reactioη5 employing the neutral ligand, where R4 is hydrogen, in combination with the metal precursors M(NR32)4 or MR34 can be employed. These reactioη5 are conducted in an inert solvent such as a hydrocarbon solvent or a etheral solvent in the temperature range of -100 9C to 150 0C.


An especially useful metal complex precursor reagent corresponds to the formula 3:
Formula 3 wherein M is zirconium, R1 and LB are as previously
defined and Y3 each occurrence is chloride. Employment of this precursor in the reaction with ligands of this invention renders the resulting metal complex in high racemic purity, which is especially useful in the stereospecific polymerization of a-olefins.
Alternatively, where 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.
The recovery of the desired Group 4 transition metal complex is accomplished by separation of the product from any alkali metal or alkaline earth metal salts and devolatilization of the reaction medium. Extraction into a secondary solvent may be employed if desired. Alternatively, if the desired product is an insoluble precipitate, filtration or other separation techniques may be employed. Final purification, if required, may be accomplished by recrystallization from an inert solvent, employing low temperatures if needed.
The complexes are rendered catalytically active by combination with acitvating cocatalysts or use of activating techniques that are previously known in the art for use with Group 4 metal olefin polymerization complexes. Suitable activating cocatalysts for use herein include polymeric or oligomeric alumoxanes, especially methylalumoxane, triisobutyl aluminum modified methylalumoxane, or isobutylalumoxane; neutral Lewis acids, such as C1-30 hydrocarbyl substituted Group
13 compounds, especially tri(hydrocarbyl)aluminunv or tri(hydrocarbyl)boron compounds and halogenated (including perhalogenated) derivatives thereof, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially perfluorinated tri(aryl)boron compounds, and most especially tris(pentafluoro-phenyl)borane; nonpolymeric, compatible, noncoordinating, ion forming compounds (including the use of such compounds under oxidizing conditions), especially the use of ammonium-, phosphonium-, oxonium-. carbonium-, silylium- or sulfonium- salts of compatible, noncoordinating anions, or ferrocenium salts of compatible, noncoordinating anions; bulk electrolysis (explained in more detail

hereinafter); and combinatioη5 of the foregoing activating cocatalysts and techniques. The foregoing activating cocatalysts and activating techniques have been previously taught with respect to different metal complexes in the following references: EP-A-277,003, US-A-5,153,157, US-A-5,064,802, US-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. US-A-5.919,983, US-A-5,783,512. WO 99/15534, and USSN 09/251,664, filed February 17, 1999.
Combinatioη5 of neutral Lewis acids, especially the combination of a trialkylaluminum compound having from 1 to 4 carboη5 in each alkyl group and a halogenated tri(hydrocarbyl)boron compound having from 1 to 20 carboη5 in each hydrocarbyl group, especially tris(pentafluorophenyl)borane, further combinatioη5 of such neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane, and combinatioη5 of a single neutral Lewis acid, especially tris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxane are especially desirable activating cocatalysts. Preferred molar ratios of Group 4 metal complex;tris(pentafluoro-phenylboraneralumoxane are from 1:1:1 to 1:10:30, more preferably from 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 which is a Broη5ted acid capable of donating a proton, and a compatible, noncoordinating anion. A". As used herein, the term "noncoordinating" meaη5 an anion or substance which either does not coordinate to the Group 4 metal containing precursor complex and the catalytic derivative derived therefrom, or which is only weakly coordinated to such complexes thereby remaining sufficiently labile to be displaced by a neutral Lewis base. A noncoordinating anion specifically refers to an anion which when functioning as a charge balancing anion in a cationic metal complex does not traη5fer an anionic substituent or fragment thereof to said cation thereby forming neutral complexes. "Compatible anioη5" are anioη5 which are not degraded to neutrality when the initially formed complex decomposes and are noninteη5ering with desired subsequent polymerization or other uses of the complex.
Preferred anioη5 are those containing a single coordination complex comprising a charge-bearing metal or metalloid core which anion is capable of balancing the charge of the active catalyst species (the metal cation) which may be formed when the two components are combined. Also, said anion should be sufficiently labile to be displaced by olefinic, diolefinic and acetylenically uη5aturated 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. Compounds containing anioη5 which comprise coordination complexes containing a single metal or metalloid atom are, of course, well known and many, particularly such compounds containing a single boron atom in the anion portion, are available commercially.
Preferably such cocatalysts may be represented by the following general formula:
(L--H)/ (A)d-wherein:
L" is a neutral Lewis base;
(L*-H)+ is a conjugate Broη5ted acid of L*;
Ad- is a noncoordinating, compatible anion having a charge of d-, and
d is an integer from 1 to 3.
More preferably Ad corresponds to the formula: [M"Q4]"; wherein:
M" is boron or aluminum in the +3 formal oxidation state; and
Q independently each occurrence is selected from hydride, dialkylamido, halide, hydrocarbyl, hydrocarbyloxide, halo-substituted hydrocarbyl, halo-substituted hydrocarbyloxy, and halo- substituted silylhydrocarbyl radicals (including perhalogenated hydrocarbyl- perhalogenated hydrocarbyloxy- and perhalogenated silylhydrocarbyl radicals), said Q having up to 20 carboη5 with the proviso that in not more than one occurrence is Q halide. Examples of suitable hydrocarbyloxide Q groups are disclosed in U. S. Patent 5,296,433.
In a more preferred embodiment, d is one, that is, the counter ion has a single negative charge and is A. Activating cocatalysts comprising boron which are particularly useful in the preparation of catalysts of this invention may be represented by the following general formula:
(L"-H)+(BQ4)-; wherein:
L* is as previously defined;
B is boron in a formal oxidation state of 3; and
Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-, fluorinated hydrocarbyloxy-, or fluorinated silylhydrocarbyl- group of up to 20 nonhydrogen atoms, with the proviso that in not more than one occasion is Q hydrocarbyl.

Preferred Lewis base salts are ammonium salts, more preferably trialkylammonium salts containing one or more C12-40 alkyl groups. Most preferably, Q is each occurrence a fluorinated aryl group, especially, a pentafluorophenyl group.
Illustrative, but not limiting, examples of boron compounds which may 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, tri(n-butyl)ammonium tetrakis(pentafluorophenyl) borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl) borate, N,N-dimethyianilinium tetrakis(pentafluorophenyl) borate, N,N-dimethylanilinium n-butyltris(pentafluorophenyl) borate, N,N-dimethylanilinium benzyltris(pentafluorophenyl) borate, N.N-dimethylanilinium tetrakis(4-(t-butyldimethylsilyl)-2, 3, 5, 6-tetrafluorophenyl) borate,
N.N-dimethylanilinium tetrakis(4-(trη5opropylsilyl)-2, 3, 5, 6-tetrafluorophenyl) borate. N.N-dimethylanilinium pentafluorophenoxytris(pentafluorophenyl) borate, N.N-diethylanilinium tetrakis(pentafluorophenyl) borate, N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl) borate, dimethyltetradecylammonium tetrakis(pentafluorophenyl) borate, dimethylhexadecylammonium tetrakis(pentafluorophenyl) borate, dimethyloctadecylammonium tetrakis(pentafluorophenyl) borate, methylditetradecylammonium tetrakis(pentafluorophenyl) borate, methylditetradecylammonium (hydroxyphenyl)tris(pentafluorophenyl) borate, methylditetradecylammonium (diethylaluminoxyphenyl)tris(pentafluorophenyl) borate, methyldihexadecylammonium tetrakis(pentafluorophenyl) borate, methyldihexadecylammonium (hydroxyphenyl)tris(pentafluorophenyl) borate, methyldihexadecylammonium (diethylaluminoxyphenyl)tris(pentafluorophenyl) borate, methyldioctadecylammonium tetrakis(pentafluorophenyl) borate, methyldioctadecylammonium (hydroxyphenyl)tris(pentafluorophenyl) borate, methyldioctadecylammonium (diethylaluminoxyphenyl)tris(pentafluorophenyl) borate, mixtures of the foregoing, dialkyl ammonium salts such as:

di-(i-propyl)ammonium tetrakis(pentafluorophenyl) borate, methyloctadecylammonium tetrakis(pentafluorophenyl) borate, methyloctadodecylammonium tetrakis(pentafluorophenyl) borate, and dioctadecylammonium tetrakis(pentafluorophenyl) borate; tri-substituted phosphonium salts such as: triphenylphosphonium tetrakis(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 methylcotadecylsulfonium tetrakis(pentafluorophenyl) borate.
Preferred (L*-H)+ cations are methyldioctadecylammonium and dimethyloctadecylam mon ium.
Another suitable ion forming, activating cocatalyst comprises a salt of a cationic oxidizing agent and a noncoordinating. compatible anion represented by the formula:

wherein:
Ox** is a cationic oxidizing agent having a charge of e+;
e is an integer from 1 to 3; and
Ad" and d are as previously defined.
Examples of cationic oxidizing agents include: ferrocenium, hydrocarbyl-substituted ferrocenium, Ag* or Pbt2. Preferred embodiments of A0" are those anions previously defined with respect to the Bronsted acid containing activating cocatalysts, especially tetrakis(pentafluorophenyl)borate.
Another suitable ion forming, activating cocatalyst comprises a compound which is a salt of a carbenium ion and a noncoordinating, compatible anion represented by the formula:
©* A" wherein:
©* is a Ci.20 carbenium ion; and

A is as previously defined. A preferred carbenium ion is the trityl cation, that is triphenylmethylium.
A further suitable ion forming, activating cocatalyst comprises a compound which is a salt of a silylium ion and a noncoordinating, compatible anion represented by the formula:

wherein:
R is C,10 hydrocarbyl, and X", q and A are as previously defined.
Preferred silylium salt activating cocatalysts are trimethylsilylium tetrakispentafluorophenylborate, triethylsilylium tetrakispentafluorophenylborate and ether substituted adducts thereof. Silylium salts have been previously generically disclosed in J. Chem Soc. Chem. Comm., 1993, 383-384, as well as Lambert, J. B., et al., Organometallics, 1994, 13, 2430-2443. The use of the above silylium salts as activating cocatalysts for addition polymerization catalysts is disclosed in US serial number 304,314, filed September 12,1994, published in equivalent form as WO96/08519 on March 21, 1996.
Certain complexes of alcohols, mercaptans, silanols, and oximes with tris(pentafluorophenyl)borane are also effective catalyst activators and may be used according to the present invention. Such cocatalysts are disclosed in USP 5,296,433.
Another class of suitable catalyst activators are expanded anionic compounds
corresponding to the formula:
wherein:
A1 is a cation of charge +aZ" is an anion group of from 1 to 50, preferably 1 to 30 atoms, not counting hydrogen atoms, further containing two or more Lewis base sites;
J1 independently each occurrence is a Lewis acid coordinated to at least one Lewis base site of Z1. and optionally two or more such J1 groups may be joined together in a moiety having multiple Lewis acidic functionality,
j1 is a number from 2 to 12 and
a1, b1, c1 and d" are integers from 1 to 3, with the proviso that a1 x b" is equal to c1 xd1
The foregoing cocatalysts (illustrated by those having imidazolide, substituted imidazolide. imidazolinide, substituted imidazolinide, benzimidazolide, or substituted benzimidazolide anions) may be depicted schematically as follows:




wherein:
A,+ is a monovalent cation as previously defined, and preferably is a trihydrocarbyl ammonium cation, containing one or two C10-40 alkyl groups, especially the methylbis(tetradecyl)ammonium- or methylbis(octadecyl)ammonium- cation,
R8, independently each occurrence, is hydrogen or a halo, hydrocarbyl, halocarbyl, halohydrocarbyl, silylhydrocarbyl. or silyl, (including mono-, di- and tri(hydrocarbyl)silyl) group of up to 30 atoms not counting hydrogen, preferably C1-20 alkyl, and
J" is tris(pentafluoropheny1)borane or tris(pentafluorophenyl)aluminane.
Examples of these catalyst activators include the trihydrocarbylammonium-. especially, methylbis(tetradecyl)ammonium- or methylbis(octadecyl)ammonium- salts of:
bis(tris(pentafluorophenyl bis(tris(pentafluorophenyl bis(tris(pentafluorophenyl bis(tris(pentafluorophenyl bis(tris(pentafluorophenyl bis(tris(pentafluorophenyl bis(tris(pentafluorophenyl bis(tris(pentafluorophenyl bis(tris(pentafluorophenyl bis(tris(pentafluorophenyl bis(tris(pentafluorophenyl bis(tris(pentafluorophenyl bis(tris(pentafluorophenyl bis(tris(pentafluorophenyl bis(lris(pentafluorophenyl bis(tris(pentafluorophenyl bis(tris(pentafluorophenyl

)borane)imidazolide.
)borane)-2-undecylimidazolide,
)borane)-2-heptadecylimidazolide,
)borane)-4,5-bis(undecyl)imidazolide,
)borane)-4,5-bis(heptadecyl)imidazolide,
)borane)imidazolinide,
)borane)-2-undecylimidazolinide,
)borane)-2-heptadecylimidazolinide.
)borane)-4,5-bis(undecyl)imidazolinide,
)borane)-4,5-bis(heptadecyl)imidazolinide,
)borane)-5,6-dimethylbenzimidazolide,
)borane)-5,6-bis(undecyl)benzimidazolide,
)alumane)imidazolide,
)alumane)-2-undecylimidazolide,
)alumane)-2-heptadecylimidazolide,
)alumane)-4,5-bis(undecyl)imidazolide.
)alumane)-4,5-bis(heptadecyl)imidazolide.

bisltris(pentafluorophenyl)a!umane)imidazolinide,
bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolinide,
bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolinide,
bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolinide,
bis(tris(pentafluorophenyl)alumane)"4,5-bis(heptadecyl)imidazolinide,
bis(tris(pentafluorophenyl)alumane)-5,6-dimethylbenzimidazolide, and
bis(tris(pentafluorophenyl)alumane)-5,6-bis(undecyl)benzimidazolide.
The molar ratio of catalyst/cocatalyst employed preferably ranges from 1:10,000 to 100:1, more preferably from 1:5000 to 10:1, most preferably from 1:1000 to 1:1. Alumoxane, when used by itself as an activating cocatalyst, is employed in large quantity, generally at least 100 times the quantity of metal complex on a molar basis. Tris(pentafluorophenyl)borane, where used as an activating cocatalyst is employed in a molar ratio to the metal complex of form 0.5:1 to 10:1, more preferably from 1:1 to 6:1 most preferably from 1:1 to 5:1. The remaining activating cocatalysts are generally employed in a molar ratio to the metal complex from 0.9:1 to 3:1, and preferably in approximately an equimolar quantity with the metal complex, that is from 1.1 to 1.5:1.
The catalyst composition may be prepared and employed as a heterogeneous catalyst by adsorbing, depositing or chemically attaching the requisite components on an inert inorganic or organic particulated solid. Examples of such solids include, silica, silica gel, alumina, clays, expanded clays (aerogels), aluminosilicates, trialkylaluminum compounds, and organic or inorganic polymeric materials, especially polyolefiη5. In an preferred embodiment, a heterogeneous catalyst is prepared by reacting an inorganic compound, preferably a tri(Ci.4 alkyl aluminum compound, with an activating cocatalyst, especially an ammonium salt of a hydroxyaryl(trispenta-fluorophenyl)borate. such as an ammonium salt of (4-hydroxy-3,5-ditertiarybutylphenyl)tris-(pentafluorophenyl)borate or (4-hydroxyphenyl)-tris(pentafluorophenyl)borate. This activating cocatalyst is deposited onto the support by coprecipitating, imbibing, spraying, or similar technique, and thereafter removing any solvent or diluent. The metal complex is added to the support, also by adsorbing, depositing or chemically attaching the same to the support, either subsequently, simultaneously or prior to addition of the activating cocatalyst.
The catalysts, preferably supported in any of the foregoing methods, may be used to polymerize ethylenically and/or acetylenically uη5aturated monomers having from 2 to 8 carbon atoms either 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 monomers include 1,3-butadiene, ethylidenenorbornene, and mixtures thereof. Preferred monomers include ethylene, or a mixture of C2-6 α-olefiη5.
Long chain macromolecular α-olefins are vinyl terminated polymeric amnants formed in situ, especially during continuous or semi-continuous polymerization reactioη5. Under suitable processing conditioη5 such long chain macromolecular units are readily polymerized into the polymer product along with ethylene and other short chain olefin monomers to give small quantities of long chain branching in the resulting polymer. Such polymers possess improved rheological properties, especially improved extrusion characteristics compared to polymers containing relatively less long chain branching. One analytical measurement that may indicate the presence of long chain branching in an olefin polymer is the presence of an elevated 110/12 or an elevated 121/12 value, while possessing narrow molecular weight distribution as determined by Mw/Mn, compared to polymers not having long chain branching. Preferred are such polymers having Mw/Mn less than 3.5, especially less than 3.0, especially less than 2.8 and 110/12 of greater than 10, preferably greater than 20, most preferably greater than 30.
In general, the polymerization may be accomplished at conditioη5 well known in the prior art for gas phase polymerization reactioη5, that is, temperatures from 0-250°C, preferably 60 to 150°C, more preferably from 70 to 1109C and pressures from atmospheric to 10.000 atmospheres. A support, especially silica, alumina, or a polymer (especially poly(tetrafluoroethylene) or a polyolefin) may be employed, and desirably is employed to obtain a desired, particulated, polymer morphology. The support is preferably employed in an amount to provide a weight ratio of catalyst (based on metal):support from 1:100,000 to 1:10, more preferably from 1:50,000 to 1:20. and most preferably from 1:10,000 to 1:30. In most polymerization reactioη5 the molar ratio of catalyst:polymerizable compounds employed is from 1012:1 to 10"":1, more preferably from 10"9:1 to 105:1.
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 and moisture free atmosphere. Preferably, therefore, the reactioη5 are peη5ormed in the presence of an dry, inert gas such as, for example, nitrogen.
Gas phase processes for the polymerization of olefiη5, especially the homopolymerization and copolymerization of ethylene and propylene, and the

copolymerization of ethylene with higher α-olefiη5 are well known in the art. The polymerization may be carried out as a batchwise or a continuous polymerization process A continuous process is preferred, in which event catalyst, ethylene, comonomer, and optionally solvent are continuously supplied to the reaction zone and polymer product continuously removed, or intermittently removed therefrom. The gas phase process employed can be, for example, of the type which employs a mechanically stirred bed or a gas fluidized bed as the polymerization reaction zone. Pi ef erred is the process wherein the polymerization reaction is carried out in a vertical cylindrical polymerization reactor containing a fluidized bed of polymer particles supported above a peη5orated plate, the fluidization grid, by a flow of fluidization gas.
Cooling of the reactor may be provided by the use of recycle gas, which is fed as a volatile liquid to the bed to provide an evaporative cooling effect. The volatile liquid employed in this case can be, for example, a volatile inert liquid, for example, a saturated hydrocarbon having 3 to 8, preferably 4 to 6, carbon atoms. In the case that the monomer or comonomer itself is a volatile liquid (or can be condeη5ed to provide such a liquid) this can be fed to the bed to provide an evaporative cooling effect. The volatile liquid evaporates in the hot fluidized bed to form gas which mixes with the fluidizing gas. If the volatile liquid is a monomer or comonomer, it will undergo some polymerization in the bed. The evaporated liquid then emerges from the reactor as part of the hot recycle gas, and enters the compression/heat exchange part of the recycle loop. The recycle gas is cooled in the heat exchanger and, if the temperature to which the gas is cooled is below the dew point, liquid will condeη5e from the gas. This liquid is desirably recycled continuously to the fluidized bed. It is possible to recycle the condeη5ed liquid to the bed as liquid droplets carried in the recycle gas stream. This type of process is described, for example in 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 to reinject this liquid directly into the bed, preferably using a method which 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 monomer and one or more comonomers on the fluidized particles of catalyst, supported catalyst or prepolymer within the bed. Start-up of the polymerization reaction is desirably achieved using a bed of preformed polymer particles, which are preferably similar to the target polyolefin. and conditioning the bed according to techniques that are well known in the art. Such processes are used

commercially on a large scale for the manufacture of high deη5ity polyethylene (HOPE), medium deη5ity polyethylene (MDPE), linear low deη5ity polyethylene (LLDPE) and polypropylene.
The gas employed to fluidize the bed comprises the monomer or monomers to be polymerized, and also serves as a heat exchange medium to remove the heat of reaction from the bed. The hot gases emerge from the top of the reactor, normally via a tranquilization zone, also known as a velocity reduction zone, having a larger cross-sectional area than the fluidized bed and wherein fine particles entrained in the gas stream have an opportunity to gravitate back into the bed. It can also be advantageous to use a cyclone to remove fine particles from the hot gas stream. The gas is then normally recycled to the bed by meaη5 of a blower or compressor and one or more heat exchangers to strip the gas of the heat of polymerization. The produced polymer is discharged continuously or discontinuously from the fluidized bed as desired.
Typically the molar ratio of comonomer to monomer used in the polymerization depends upon the desired deη5ity for the composition being produced and is desirably about 0.5 or less. Desirably, when producing materials with a deη5ity range of from 0.91 to 0.93 the comonomer to monomer ratio is less than 0.2, preferably less than 0.05, even more preferably less than 0.02, and may even be less than 0.01. Hydrogen may be added to the reaction in order to control the molecular weight and melt index of the polymer. Typically, the ratio of hydrogen to monomer is less than about 0.5, preferably less than 0.2, more preferably less than 0.05, even more preferably less than 0.01.
A number of patents and patent applicatioη5 describe gas phase processes which are adaptable for use in the process of this invention, particularly, USP"s 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. EPA-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
The skilled arη5an will appreciate that the invention disclosed herein may be practiced in the absence of any component which has not been specifically disclosed. The following examples are provided as further illustration of the invention and are not to be coη5trued as limiting. Unless stated to the contrary all parts and percentages are expressed on a weight basis. The term "overnight", if used, refers to a time of approximately 16-18 hours, the term "room temperature", refers to a temperature of

about 20-25 °C, and the term "mixed alkanes" refers to a commercially obtained mixture of C6.8 aliphatic hydrocarboη5 available under the trade designation Isopar E®, from Exxon Chemicals Inc.
lH (300 MHz) and 13C NMR (75 MHz) spectra were recorded on a Varian XL-300 spectrometer. "H and ,13C NMR spectra are referenced to the residual solvent peaks and are reported in ppm relative to tetramethylsilane. All J values are given in Hz. Tetrahydrofuran (THF), diethylether, toluene, and hexane were used following passage through double columη5 charged with activated alumina and a purifying catalyst (Q-5® available from Englehardt Chemicals Inc.) The compounds BCI3-SMe2, BBr3-SMe2, B(NMe2)3l n-BuLi were all used as purchased from Aldrich. The compound TiCI3(THF)3 was prepared as described in the literature. All syntheses were peη5ormed under dry nitrogen or argon atmospheres using a combination of glove box and high vacuum techniques.
Example 1 Dichloro-[1,2-Bis(2,6-dη5opropylanilide)-1,2-bis(dimethylamido)diborane] titanium

1A) Preparation of Chlorobis(dimethylamido)borane, (modification of Chavant, P. Y. Vaultier, M. J. Organomet. Chem. 1993, 455, 37-46)
BC!3-SMe2 (62.000 g, 345.78 mmol) and B(NMe2)3 (98.921 g, 691.56 mmole) were stirred together at room temperature overnight under a nitrogen bubbler. The mixture was then heated to reflux for one hour to drive off any residual SMe2. Allowing the pale yellow liquid to stir to room temperature resulted in the isolation of the desired product cleanly (44.979 g, 99.9 percent yield).
"HNMR(C6D6): 5 2.49 (s, 12 H). ,3C NMR (C6D6): 5 39.86. 1B) Preparation of Tetrakis(dimethylamido)diborane (modification of Noth, H; Meister. W. Z Natuη5orsch., Teil B 1962, 17, 714)

Chlorobis(dimethylamido)borane (30.000 g, 223.19 mmol) was refluxed in hexane (200 ml) as Na/K alloy (Na (1.539 g , 66.96 mmol)/8.726 g K (8.726 g, 223.19 mmol)] was added dropwise to the solution. After the first several drops the reaction initiated as evidenced by a sudden increase in the reflux. The heat was then turned off and the alloy added slowly so as to maintain a reflux. After the addition was complete, the reaction mixture was heated to reflux for an additional hour and then stirred at room temperature for three hours. The mixture was then filtered through a pad of diatomaceous earth and the volatiles removed resulting in the isolation of a yellow liquid. Fractional vacuum distillation resulted in the isolation of the desired compound as a pale yellow liquid (7.756 g, 35.1 percent yield).
"H NMR (C6D6): 6 2.74 (s, 24 H). 13C NMR (C6D6): 5 41.34. 1C) Preparation of Bis(dimethylamido)diborondichloride (modification of Noth, H; Meister, W. Z. Naturiorsch., Teil B1962, 17, 714)
Tetrakis(dimethylamido)diborane (7.76 g, 39.29 mmol) was stirred in diethylether (100 ml) at -78 °C as HCI (157 mmol, 157 ml of 1.0 M solution in diethylether) was added dropwise. This mixture was then allowed to stir for six hours at room temperature. After the reaction period the volatiles were removed and the residue extracted and filtered using hexane. Removal of the hexane resulted in the isolation of a yellow oil. Fractional vacuum distillation resulted in the isolation of the desired compound as a pale yellow liquid (4.72 g, 66.7 percent yield).
"H NMR (C6D6): 5 2.40 (s, 6 H), 2.50 (s, 6 H). ,3C NMR (C6D6): 8 37.62, 41.78. 1D) Preparation of 2,6-Dη5opropylaniline, lithium salt
n-BuLi (56.4 mmol, 35.3 ml of 1.60 M solution in hexane) was added dropwise to a solution of 2,6-dη5opropylaniline (10.0 g, 56.4 mmol) in hexane (100 ml). This mixture was allowed to stir for 3 hours during which time a whjte precipitate formed. After the reaction period the mixture was filtered and the white salt washed with hexane and dried under vacuum and used without further purification or analysis (9.99 g, 96.7 percent). 1E) Preparation of 1,2-Bis(2,6-dη5opropylanilide)-1,2-bis(dimethylamido)diborane
Bis(dimethylamido)diborondichloride (2.35 g. 13.0 mmol) in diethylether (10 ml) was added dropwise to a solution of 2.6-dη5opropylaniline, lithium salt (4.77 g, 26.0 mmol) in diethylether (50 ml) at 0°C. This mixture was then allowed to stir overnight at room temperature. After the reaction period the volatiles were removed and the residue extracted and filtered using hexane. Removal of the hexane resulted in the isolation of a the desired product as a white solid (5.32 g, 88.9 percent yield).

"H NMR (C6D6. RT): 5 0.9-1.4 (br m, 24 H), 2.3 (s, 6 H), 2.8 (s. 6 H), 3.7 (s, 2 H). 7.0(brs,6H).
1F) Preparation of 1,2-Bis(2,6-dη5opropylanilideH,2-bis(dimethylamido)diborane, dilithium salt
1,2-Bis(2,6-dη5opropylanilide)-1,2-bis(dimethylamido)diborane (1.82 g, 3.95 mmol) was stirred in hexane (75 ml) as n-BuLi (7.91 mmol, 4.94 ml of 1.60 M solution in hexane) was added dropwise. This mixture was then allowed to stir overnight. After the raaction period the mixture was filtered and the salt washed well with hexane and dried under vacuum resulting in the isolation of the desired product as a white powder (1.69 g, 90.4 percent yield).
1G) Preparation of Dichloro-[1,2-Bis(2,6-dη5opropylanilide)-1,2-bis(dimethylamido)diborane]titanium
1,2-Bis(2,6-dη5opropylanilide)-1,2-bis(dimethylamido)diborane, dilithium salt (0.60 g, 1.27 mmol) in THF (20 ml) was added dropwise to a slurry of TiCI3(THF)3 (0.47 g, 1.27 mmol) in THF (50 ml) at 0°C. This mixture was then allowed to stir at room temperature for 45 minutes. PbCI2 (0.177 g, 0.640 mmol) was then added as a solid and the mixture allowed to stir for an additional 30 minutes. After the reaction period the volatiles were removed and the residue extracted and filtered using hexane. Concentration of the hexane and cooling to -10 °C overnight resulted in the formation of orange X-ray quality crystals (0.156 g, 21.3 percent yield).
"H NMR (C6D6): 5 1.23 (d, 3JHH= 6.6 Hz, 6 H), 1.45 (d, 3JHH= 6.6 Hz, 6 H), 2.17 (s. 6 H). 2.76 (s, 6 H), 3.53 (septet, 3JHH= 6.6 Hz, 4 H). 7.11 (s. 6 H)
Example 2 Dichloro [1,2-Bis(2,6-dη5opropylanilide)-1,2-bis(dimethylamido)diborane]
titanium (alternated preparation)
2A) Preparation of Chlorobis(dimethylamido)borane.
BCI3-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 bubbler. The mixture was then heated to reflux for one hour to drive off any residual SMe2. Allowing the pale yellow liquid to stir to room temperature resulted in the isolation of the desired product (139.436 g, 93.3 percent yield). "H NMR (C6D6): 6 2.49 (s, 12 H). ,3C NMR (C6D6): 5 39.86. 2B) Preparation of Tetrakis(dimethylamido)diborane via CIB(NMe)2.
Chlorobis(dimethylamido)borane (30.000 g, 223.19 mmol) was refluxed in hexane (200 ml) as Na/K alloy [Na (1.539 g , 66.96 mmol)/8.726 g K (8.726 g. 223.19 mmol)] was added dropwise to the solution. After the first several drops the reaction

initiated as evidenced by a sudden increase in the reflux. The heat was then turned off and the alloy added slowly so as to maintain a reflux. After the addition was complete, the reaction mixture was heated to reflux for an additional hour and then stirred at room temperature for three hours. The mixture was then filtered through a diatomaceous earth pad and the volatile components were removed resulting in the isolation of a yellow liquid. Fractional vacuum distillation resulted in the isolation of the desired compound as a pale yellow liquid (7.756 g, 35.1 percent yield). "H NMR (C6D6): 5 2.73 (s. 24 H). ,3C NMR (C6D6): 5 41.37. 2C) Preparation of Tetrakis(dimethylamido)diborane via Bis(catecholato)diboron.
Lithium dimethylamide (10.70 g, 210.0 mmol) was added slowly as a solid to a solution of bis(catecholato)diboron (10.00 g, 42.00 mmol) in diethylether (200 ml) at -20°C. This mixture was then allowed to stir for an additional 40 hours at room temperature. After the reaction period the ether was removed under vacuum and the residue extracted and filtered using hexane. Removal of the hexane resulted in the isolation of a yellow oil. Fractional vacuum distillation 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)diborondichloride.
Tetrakis(dimethylamido)diborane (7.756 g, 39.19 mmol) was stirred in diethylether (100 ml) at -78°C as HCI (156.75 mmol, 156.75 ml of 1.0 M solution in diethylether) was added dropwise. This mixture was then allowed to stir for six hours at room temperature. After the reaction period the volatile components were removed and the residue extracted and filtered using hexane. Removal of the hexane resulted in the isolation of a yellow oil. Fractional vacuum distillation resulted in the isolation of the desired compound as a pale yellow liquid (4.722 g, 66.7 percent yield). "H NMR (C6D6): 5 2.40 (s, 6 H). 2.50 (s, 6 H). 13C NMR (C6D5): 5 37.62. 41.78. 2E) Preparation of 2,6-Dη5opropylaniline, lithium salt.
n-BuLi (56.40 mmol, 35.25 ml of 1.6 M solution in hexane) was added dropwise to a solution of 2,6-dη5opropylaniline (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 the mixture was filtered and the white salt washed with hexane and dried under vacuum and used without further purification or analysis (9.988 g. 96.7 percent yield). 2F) Preparation of 1,2-Bis(2,6-dη5opropylanilide)-1.2-bis(dimethylamido)diborane.
Bis(dimethylamido)diborondichloride (2.350 g, 13.00 mmol) in diethylether (10 ml) was added dropwise to a solution of 2,6-dη5opropylaniline, lithium salt (4.765 g, 26.01 mmol) in diethylether (50 ml) at 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 extracted and filtered using hexane. Removal of the hexane resulted in the isolation of a the desired product as a white solid (5.322 g, 88.9 percent yield).
"H NMR (toluene-d8): 6 0.9-1.4 (br m. 24 H), 2.3 (s, 6 H), 2.8 (s, 6 H). 3.7 (s. 2 H), 7.0 (br s, 6 H). ,3C NMR (toluene-da): 5 22.51, 24.03 (br), 28.17, 36.82, 42.67. 123.19, 124.78, 140.71, 145.02 (br). MS(EI): m/z460.4025 (M-H)\ calcd. (M-H)* 460.4026. 2G) Preparation of 1,2-Bip(2,6-dη5opropylani!ide)-1,2-bis(dimeη5iylamido)diborane, dilithium salt.
1,2-Bis(2,6-dη5opropylanilide)-1,2-bis(dimethylamido)diborane (1.820 g, 3.950 mmol) was stirred in hexane (75 ml) as n-BuLi (7.91 mmol, 4.94 ml of 1.6 M solution in hexane) was added dropwise. This mixture was then allowed to stir overnight-After the reaction period the mixture was filtered and the salt washed well with hexane and dried under vacuum resulting in the isolation of the desired product as a white powder (1.6878 g, 90.4 percent yield).
"H NMR (THF-d8): 5 1.04 (d, 3JHH=6.9 HZ, 6 H), 1.18 (d, 3JHH= 6.9 Hz, 6 H), 2.45 (s, 12 H), 3.66 (septet. 3JHH= 6.9 Hz, 4 H), 6.29 (t, 3JH= 7.5 Hz, 2 H), 6.73 (d, 3JHH= 7.5 Hz, 4 H). 13C NMR (THF-d8): 5 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-dη5opropylanilide)-1,2-bis(dimethylamido)diborane]titaniurn.
1,2-Bis(2,6-diisopropylaniiide)-1,2-bis(dimethylamido)diborane, dilithium salt (0.600 g, 1.27 mmol) in THF (20 ml) was added dropwise to a slurry of TiCI3(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. PbCI2 (0.177 g, 0.640 mmol) was then added as a solid and the mixture allowed to stir for an additional 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 g, 21.3 percent yield).
"H NMR (toluene-dg): 5 1.23 (d, 3JHH= 6.6 Hz, 6 H), 1.45 (d. 3JHH= 6.6 Hz, 6 H), 2.17 (s, 6 H), 2.76 (s. 6 H). 3.53 (septet, 2JHH= 6.6 Hz, 4 H), 7.11 (s. 6 H). ,JC NMR (toluene-d8): 5 24.94, 24.67, 29.48, 39.33, 42.93, 124.08 (br), 17.23. 150.64. MS(EI):

m/z 578.2789 (M)*. calcd. (M)* 578.2781. Anal. Calcd. For C29η46B2N2TiCI2: 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-dη5opropylanilide)-1,2-bis(dimethylamido)diborane] titanium
Dichloro-[1,2-Bis(2,6-dη5opropylanilide)-1,2-bis(dimethylamido)diborane] titanium (Example 2) (0.272 g, 0.470 mmol) was stirred in diethylether (40 ml) as MeMgBr (0.940 mmol, 0.313 ml of 3.0 M solution in diethylether) was added dropwise. This mixture was allowed to stir for one hour. After the reaction period the volatiles were removed and the residue extracted and filtered using hexane. Removal of the hexane resulted in the isolation of the desired product as a dark yellow oil (0.209 g, 82.5 percent yield).
"H NMR (C6D6): 5 1.05 (s, 6 H), 1.21 (d, 3JHH = 6.9 Hz, 16 H), 1.32 (d, 3^H = 6.3 Hz, 16 H), 2.19 (s. 6 H), 2.69 (s. 6 H), 3.58 (or. 2 H), 7.0-7.2 (m, 6 H). 13C NMR (C6D6): 5 24.06, 24.83, 29.31, 39.58, 42.93, 57.38, 123.97, 125.18, 139.5 (br), 149.45.
Example 4 Dibenzyl [1,2-Bis(2,6-dη5opropylanilide)-1,2-bis(dimethylamido)diborane] zirconium
Zirconium tetrachloride (0.100 g, 0.440 mmol) and zirconium tetrabenzyl (0.192 g, 0.440 mmol) were stirred together in diethylether (30 ml) for 1 hour. 1,2-Bis(2,6-dη5opropylanilide)-1,2-bis(dimethylamido)diborane, dilithium salt (Example 2G) (0.400 g, 0.842 mmol) in diethylether (30 ml) was then added dropwise and the mixture allowed to stir for 3 hours. After the reaction period the volatiles were removed under vacuum and the residue extracted 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 again filtered and the volatile components removed resulting in the isolation of the desired product as a yellow oil (0.123 g, 19.8 percent yield).
"H NMR (toluene-da): 5 1.14 (d, 3JHH= 6.6 Hz, 6 H), 1.22 (br, 6 H), 1.70 (d, 3JHH= 9.0 Hz, 2 H), 1.83 (d, 2JHH= 9.6 Hz. 2 H), 2.10 (s. 6 H) 2.71 (s. 6 H). 3.0-3.2 (br, 2 H), 3.3-3.5 (br, 2 H), 6.59 (d, 3JHH= 7.2 Hz. 4 H), 6.77 (t, 3JHH= 7.2 Hz. 2 H). 6.9-7.1 (m, 10 H). 13C NMR (toluene-da): 5 23.96 (br), 24.22 (br). 24.36 (br). 25.23 (br). 29.47, 39.72, 43.05, 62.23, 122.70, 123.73 (br), 124.08 (br). 124.33. 127.23, 130.82, 139.26 (br), 140.16 (br), 144.90, 144.92, 149.03.

Example 5 raodiisopropylamidoborane-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium η4-1.4-diphenyl-1,3-butadiene

5A) Preparation of Diisopropylaminoboron dichloride.
To a methylene chloride solution of trichloroborane (1.0 M, 100 ml, 0.10 mole) was added dropwise at -78°C diisopropylamine (13.108 ml, 0.100 mole) over a 30 minute period. The solution was allowed to stir for 1 hour, during which a white precipitate formed. The mixture was allowed to warm to room temperature, and solvent was removed under reduced pressure. The residue was dissolved in 100 ml of dry toluene, triethylamine (13.94 ml, 0.10 mole) was added and the solution was stirred overnight at room temperature. The mixture was filtered, the residue was washed with 20 ml of toluene. Solvent was removed under reduced pressure from the combined filtrates, and the resulting oil was purified by vacuum distillation (25-28 °C, 13 Pa, 0.1mm) to give 9.2g (51 percent) of product as a colorless liquid.
"H NMR (C6D6): 5 0.95 (d, 12 H). 3.63 (broad multiplet, 2 H). 5B) Preparation of N.N-diisopropylamino bis(2-methyl-4-phenylindenyl) borane
To 25 ml THF solution of N.N-diisopropylaminoboron dichloride (0.858 g, 4.72 mmole) at room temperature was added drop wise lithium (2-methyl-4-phenyl)indenide (2.00 g, 9.44 mmole in 20 ml THF). The mixture was stirred for 24 hours. Solvent was removed under reduced pressure. The residue was extracted with toluene (2x50 ml), filtered through a medium frit, and solvent was removed under reduced pressure to give a light yellow solid (2.4g, 97 percent). 5C) Preparation of rac-diisopropylaminoborane-bis-η5- (2-methyl-4-phenyl indenyl)zirconium η4-1,4-diphenyl-1,3-butadiene
N.N-diisopropylamino bis(2-methyl-4-phenylindenyl) borane (1.20 g, 2.3 mmole) was dissolved in 40 ml of toluene, 2.1 equivalents of potassium bis(trimethylsilyl) amide (0.964 g, 4.8 mmole ) was added and the resulting mixture was stirred at room temperature for 24 hours. Volatile components were removed under reduced pressure, and the resulting orange solid washed with 10 ml of hexane. filtered and pumped dry. The dipotassium salt residue (1.3 g, 95 percent, 2.18

mmole) was redissolved in 25 ml of toluene. (1,4-diphenyl-1,3-butadiene)-bis(triethylphosphine)zirconium dichloride (1.318 g, 2.18 mmole) was added and the solution stirred for 12 h at room temperature. The product mixture was filtered through diatomaceous earth filter aid and the solvent of the filtrate was removed under reduced pressure. Further purification was carried out by recrystallization from hexane to yield 0.85 g (48 percent) of the desired product as a dark red solid.
"H NMR (C6D6): 5 7.6(d, 2H); 7.42-7.00, (m, 18 H); 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 Preparation of diisopropylamidoboranebis-(cyclopentadienyl)zirconium
dichloride
6A) Diisopropylamidoboron dichloride
To a solution of BCI3 (17 g, 145 mmol) in CH2CI2 (25 ml) at -78 ° C was slowly added diisopropylamine (18.49 ml, 132 mmol). A white precipitate formed during addition. The mixture was warmed to room temperature to give a colorless solution. Solvent was removed under high vacuum at room temperature, 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, then filtered to give a red solution. Vacuum distillation (27-28 °C, 4 Pa) gave the product (15 g, 57 percent) as a colorless liquid:
"H NMR (500 MHz, CDCI3) d 1.26 (d, 12H, J = 5.8 Hz), 3.95 (br, 2H, NCH) 13C NMR (100 MHz, CDCI3) d 22.1, 49.2 (br). nB NMR (115 MHz, CDC13) 29.4. MS (El„ m/e (inteη5ity)): 181 (M+, 5), 166 (43), 124 (61), 43 (I 00)
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 slowly warmed to room temperature and stirred overnight at room temperature to give a red solution. After solvent removal, the residue was extracted with pentane (3x). filtered, pentane was then removed to give the product (0.55 g, 100 percent) as an yellow syrup.
t3B NMR (M5 MHz,C6D;) d 39.8 (major), 30.4 (minor). MS (El. m/e (inteiisity)): 241 (M+, 47), 226 (40), 176 (16). 93 (100)
GC-MS was also recorded on the reaction mixture shortly after mixing the two reagents at -78 °C, from which only cyclopentadienyldiisopropylboron chloride was detected: MS (El, m/e (inteη5ity)): 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 hr. Solvent was then removed, residue was washed with pentane to give the product (0.58 g, 91 percent) as a white solid:
"H 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
6D) Diisopropylamidoboranebis(cyclopentadienyl)zirconium dichloride
To a solution of diisopropylamidobis(cyclopentadienyl)borane (0.71 g, 2.95 mmol) in Et20 (15 ml) at -78 ° C was added lithium diisopropylamide (6.93 mmol). The mixture was stirred for 2 hr at room temperature to give a slightly turbid solution. The solution was then added to a suspeη5ion of ZrCU (0.69 g, 2.95 mmol) in Et20 (15 ml) at -78 °C. The resulting mixture was stirred overnight at room temperature to give an yellowish suspeη5ion. Solvent was partially removed and the residue concentrated and cooled to -78 ° C to give the product (0.50 g, 38 percent) as colorless crystals.
•H NMR (400 MHz, CDCI3) 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 = 2.4 Hz). ,3C NMR (100 MHz, CDCI3) d 24.6, 49.6, 111.4, 125.7. ,3B NMR (115 MHz, CDCI3) 5 37.6. HRMS (El), calculated for C16H22BNC12Zr: 399.0269, found: 399.0272.
Example 7 Preparation of meso-diisopropylamidoboranebis(inden-1-yl)zirconium
dichloride
7A) Diisopropyiamidobis(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 a solution of lithium indenide (1.50 g. 12.3 mmol) in THF (40 ml) at -78 ° C. The mixture was slowly warmed to room temperature and stirred overnight at room temperature to give a red solution. After solvent removal, the residue was extracted with CH2CI2 (3x), filtered

and the solvent removed to give the desired product (2.12 g, 100 percent) as a white solid:
"BNMR(115MHz, C6D,)d41.4. MS (El, m/e (inteη5ity)). 341 (M+. 8), 226 (100). HRMS (El), calculated for C24H28BN C24H28BN: 341.2315, found: 341.2310 7B) Meso-Diisopropylamidoboranebis(inden-1 -yl)zirconium dichloride
To a suspeη5ion of the above product (0.39 g, 1.41 mmol) in Et20 (10 ml) at -78 °C was added lithium diisopropylamide (in situ prepared from iPr2NH (2.62 mmoi) and BuLi (2.50 M, 2.62 mmol). The mixture was stirred over night at room temperature to give an orange suspeη5ion. Solvent was removed and the residue extracted with toluene, and filtered. Toluene was then removed to give an orange solid composed of a mixture of the two stereoisomers (rac/meso, ca. 6:4). Repeated recrystallization (3x) from toluene at -78 °C gave the pure meso isomer (0.08g, 14 percent) as an orange solid. M.p. = 250 -254 °C (dec).
"HNMR (500 MHz, CDCt3) 1.54(d, 6H, J= 6.6 Hz), 1.57 (d, 6H. J = 6.8 Hz). 4.27 (m, 2H, NQH). 5.91 (d, 2H, J3.0 Hz), 6.9 (m, 4H), 7.17 (t, 2H, J= 7.6 Hz), 7.31 (dd, 2H, J=8.3, 3.6 Hz), 7.53 (d, 2H, J= 8.6 Hz). 13C NMR (75 MHz, CDC!3) 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. "B NMR (115 MHz, CDCI3) 8 39.5. HRMS (El), calculated for C24H26BNC,2Zr: 499.0582, found, 499.0606. MS (El. m/e (inteη5ity)): 501 (M+, 20), 458 (7), 341 (18), 226(93). 143(80), 115(99)
*
Example 8 Preparation of rac-diisopropylamidoboranebis(inden-1-yl)zirconium bis(dimethylamide)
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 hr to give a bright red solution. The product coη5isted of two isomers with a ratio of 6.7:1. The solution was filtered, concentrated, and cooled to -78 °C to give the pure rac isomer (0.50 g, 33 percent) as red crystals. The structure was confirmed by X-ray diffraction analysis on single crystals grown from toluene / hexane at -20 °C. M.p. = 220 °C (dec).
"H 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), 7.3 7 (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. 123.1. 123.2, 124.0. 124.2. 126.3,129.1. "B NMR (115 MHz, C6D6)d 40.8. HRMS (El), calculated for

C28H38BN3aZr: 517.2206, found, 517.2217. MS (El, m/e (inteη5ity)): 517 (M+, 20), 471 (45), 429 (100). 330 (24), 226 (70)
Example 9 flac-Diisopropylamidoboranebis(inden-1-yl)zirconiurn dichloride To a solution of rac-diisopropylamidoboranebis(inden-1-yl)zirconium bis(dimethylamide) (0.50 g, 0.96 mmol) in toluene (35 ml) at room temperature was added trimethyhlsilyl chloride (2.0 ml, 15.76 mmol). The solution was stirred for 8 h at room temperature to give an orange suspeη5ion. Solvent was removed, residue was washed with pentane (2x) to give the desired product (0.40 g, 83 percent) as an orange powder. Single crystals suitable for X-ray structural analysis were grown from mixed solvents of CH2CI2 and hexane at -20 °C. M.p. = 242 °C (dec).
"H NMR (500 MHz, CDCI3) 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, 0.7 Hz), 7.07 (t, 2H, J = 7.6 Hz), 7.28 (dd, 2H, J = 7.0, 0.7 Hz), 7.3 8 (t, 2H. J = 8.0 Hz). 7.58 9d, 2H, J= 8.8 Hz). 13C NMR (75 MHz. CDCI3) 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. "B NMR (115 MHz, CDCI3) d 39.2. HRMS (El), calculated for C24H26BNCI2Zr. 499.0582, found, 499.0606. MS (El, m/e (inteη5ity)): 501 (M+, 20), 458 (7), 341 (18), 226 (93), 143 (80). 115 (99). Anal. Calculated for C24H26BNCI2Zr: 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 diisopropylamidoboranebis(inden-1-yl)zirconium dichloride (Example 6) (0.16 g, 0.32 mmol) in CH2CI2 (7 ml) was added to an autoclave reactor containing Pt02 (0.0105 g). The mixture was flushed four times with H2 (200 psi, 1 4 MPa), then charged with H2 (1500 psi, 10.4 MPa) and stirred for 15 h at room temperature to give a greenish suspeη5ion. CH2Cl2 (25 ml) was added the mixture which was then filtered. Solvent was removed under reduced pressure and the residue was washed with pentane (2x) to give diisopropylamidoboranebis(tetrahydro-inden-1-yl)zirconium dichloride (0.15 g, 92 percent) as a slightly greenish solid.
"H 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 = 4.8 Hz), 2.09 (d, 1H, J = 5.0 Hz), 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 (hept, 2H, J= 6.6 Hz). 5.01 (d, 2H, J = 2.9 Hz). 6.53 (d. 2H, J = 2.6 Hz). ,3C 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. "B NMR (115 MHz,

C6D6) d 39.2 ppm. HRMS (El) Calculated for C24l11BNCIzZr 507.1208, found 507.1198
Example 11 Preparation of rac-N,N-diisopropylamidoborane-bis-η5- (2-methyl-4-naphthyl indenyf) zirconium η4-1,4-diphenyl-1,3-butadiene.

11 A) Preparation of potassium (2-methyl-4-naphthyl) indenide
2-Methyl-4-naphthylindene (1.00 g, 3.27 mmole) was dissolved in 20 ml of toluene, potassium bis(trimethylsilyl)amide (1.05 equivalent, 3.43 mmole, 0.684 g) was added and the reaction mixture was stirred at room temperature for 24 hours, during which a yellow solid precipitated. Hexane was added (20 ml) and the mixture was stirred for 2 h. The solid product was isolated by vacuum filtration through a medium porosity frit. The solid was pumped dry giving 1.10 g, 98 percent of the desired product. 11B) Preparation of N,N-diisopropylamino bis(2-methyl-4-naphthylindeny!) borane
To a solution of N,N-diisopropylaminoboron dichloride (0.309 g, 1.70 mmole) in 25 ml of THF at room temperature was slowly added dropwise a 10 ml THF solution of potassium (2-methyl-4-naphthyl) indenide (1.00 g, 3.40 mmole). The mixture was stirred for 24 hours at room temperature, solvent was removed, and the residue was extracted with toluene (2x25 ml). The combined extracts were filtered through a medium frit, and solvent was removed under reduced pressure to give a light yellow solid (1.0 g. 95 percent).
11C) Preparation of rac-N,N-diisopropylaminoborane-bis-η5- (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 mmole) was dissolved in 20 ml of toluene, 2.05 equivalents of potassium bis(trimethylsilyl)amide (0.566 g. 2.84 mmole) was added and the reaction mixture was stirred at room temperature for 24 hours. 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 of the filtrate was removed under reduced pressure. Further purification was carried out by recrystallization from hexane to yield 0.27 g (21 percent) of the desired product as a dark red solid.
"H NMR (C6D6): 5 7.75-7.00, (mm, 30 H); 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 η4-1,4-diphenyl-1,3-butadiene

12A) Preparation of 1,2-Bis(2-methyl-4-phenyfinden-1-yl)-1,2-bis(dimethylamido)-diborane
Bis(dimethylamido)diborondichloride (0.500 g, 2.77 mmol) in diethylether (10 ml) was added dropwise to a solution of 2-methyl-4-phenylindene, lithium salt (1.407 g, 11.07 mmol) in diethylether (50 ml) at 0 °C. This mixture was stirred overnight at room temperature and the volatiles were removed. The residue was extracted using CH2CI2. Filtration and removal of the CH2CI2 resulted in the isolation of a 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 dried under vacuum. The residue was then slurried in hexane and filtered and the gold microcrystalline solid dried under vacuum (0.881 g, 97.1 percent yield).
12B) Preparation of rac-[1,2-Bis(dimethylamido)-1,2-bis(2-methyl-4-phenylindene)diborane]zirconium(trans,fraη5-1,4-diphenyl-1,3-butadiene)
1,2-Bis(dimethylamido)-1.2-bis(2-methyl-4-phenylindene)-diborane, dipotassiium salt (0.808 g, 1.35 mmol) was added slowly as a solid to a solution of (1,4-diphenylbutadiene)ZrCI2(PEt3)2 (0.819 g, 1.35 mmol) in toluene (75 ml). This

mixture was allowed to stir overnight. After the reaction period the mixture was filtered and the volatiles removed resulting in the isolation of a deep red residue. The residue was then slurried in cold hexane, filtered, and dried under vacuum resulting in the isolation of the desired product as a dark red microcrystalline solid (0.501 g, 45.3 percent yield).
"H NMR (C6D6): 5 1.1-1.2 (m, 2 H), 2.02 (s, 6 H), 2.66 (s, 6 H), 2.90 (s, 6 H). 3.3-3.4 (m, 2 H). 5.28 (s, 2 H), 6.82 (d. 3JHH= 6.6 Hz, 2 H), 6.9-7.3 (m, 14 H), 7.53 (d, 3JHH= 8.4 Hz. 2 H). ,3C NMR (C6D6): 5 15.10, 42.17, 44.36. 86.78. 93.34, 106.54. 119.17, 123.12, 123.39, 123.71, 124.26, 127.88, 128.51. 128.90, 129.34, 135.76. 140.85, 145.80.
Example 13 rac-diisopropylamidoborane-bis-η5-(2-methyl-4-phenylinden-1 -yl)hafnium

η4-1,4-diphenyl-1,3-butadiene
Hafnium tetrachloride (0.375 g, 1.17 mmol) was slurried into 40 ml of toluene. To this slurry were added triethylphosphine (0.346 ml, 2.34 mmol, via syringe), Li powder (Aldrich, low sodium, 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 then filtered using a medium porosity frit and diatomaceous earth pad to remove the unreacted Li metal. To the filtrate was added dipotassium diisopropylamidobis(1-(2-methyl-4-phenylindenide))borane, K2(Pr2NB(2-Me-4-Ph-indenide)2], (0.700 g. 1.17 mmol) using 10 ml of toluene to aid in the transfer. The reaction mixture was stirred for 1 hour at room temperature. The toluene was removed under reduced pressure and the reaction product was extracted with hexane (twice) and filtered (medium porosity frit with diatomaceous earth pad). Additional product was obtained by extracting the salt byproduct using toluene and refiltering using a medium porosity frit and diatomaceous earth pad.
"H NMR spectroscopic analysis indicated that the desired rac- "Pr2NB(2-Me-4-Ph-inden-1-yl)zHf(1,4-diphenyl-1,3-butadiene) isomer was largely insoluble in hexane

and that the undesired meso-isomer could be separated by repeated extraction with hexane. Final isolation and purification of raoiPr2NB(2-Me-4-Ph-inden-1-yl)2Hf(1,4-diphenyl-1,3-butadiene) was accomplished by soxhiet extraction using hexane. After the hexane extract becomes colorless the thimble was removed and dried, yielding 0.042 g of pure rao Vr2NB(2-Me-4-Ph-inden-1-yl)2Hf(1,4-diphenyl-1.3-butadiene) as determined by "H and ,3C NMR spectroscopic analysis.
"H NMR (C6D6): 5 7.6(d, 2H); 7.42-7.00, (m, 18 H); 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-η5-(2-methyl-4-phenylinden-1 -yl)zirconium Η4-1 ,4-diphenyl-1,3-butadiene
In a glove box, diisopropylamidobis(2-methyl-4-phenylinden-1-yl)borane

(0.125g. 0.240 mmole) was dissolved in 20 ml of dry THF, and 2 equivalents of potassium bis(trimethylsilyl)amide (0.500 molar solution, 0.960 ml, 0.480 mmole) was added dropwise over 10 minute period at room temperature, after which the solution was stirred for 4 hours. 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 mmole) 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 of the filtrate under reduced pressure. Further purification was carried out by recrystallization from hexane to yield the product as a dark red solid.
Example 15 Preparation of rac-{"Pr2NC(N"Pr)2}borane-bis-η5- (2-methyl-4-phenylindenyl) zirconium η4-1,4-diphenyl-1,3-butadiene.


15A) Preparation of "Pr2NC(N"Pr)2}boron dichloride.
Diisopropylcarbodiilmide was. (1.178g. 933 mmole) was dissolved in, 20 ml of toluene, cooled to 0 oC, and solid lithium diisopropylamide (1.00 g, 9.33 mmole) was added slowly to the solution over a 5 minute period. The solution was was allowed to warm to room temperature while stirring for 3 hours. This solution was subsequently added dropwise over a 30 minute period to a 1 molar heptane solution (0 oC) of boron trichloride (9.33 ml, 9.33 mmole) and allowed to warm to room temperature overnight. The solution was filtered, and solvents were removed under reduced pressure to yield 2.3 g (97 percent) of light yellow oil.
"H NMR (C6D6): 53.6-3.4 (m, 2H); 3.4-3.25 (septet, 2H); 1.43 (d, 12H); 0.8 (d, 12 H). 15B) Preparation of bis(2-methyl-4-phenylindenyl) {iPr2NC(N"Pr)2}borane
"Pr2NC(N"Pr)2}boron dichloride (0.30g, 0.97 mmole) was dissolved in 30 ml of THF, and potassium (2-methyl-4-phenyl)indenide (0.476g, 1.95 mmole) was added. The mixture was stirred for 24 hours at room temperature, followed by heating at reflux for 4 hours. The product mixture was allowed to cool to room temperature, and solvent was removed under reduced pressure. The residue was extracted with toluene (2x50 ml), filtered through a medium frit, and solvent was removed under reduced pressure to give a light yellow solid (0.533 g, 85 percent). 15C) Preparation of rac-{"Pr2NC(N"Pr)2}borane -bis-if- (2-methyl-4-naphthyl indenyl) zirconium Η4~1 ,4-diphenyl-1,3-butadiene.
Bis(2-methyl-4-phenylindenyl) {"Pr2NC(N"Pr)2}borane (0.533 g, 0.82 mmole) was dissolved in 20 ml of toluene, 2.00 equivalents of potassium bis(trimethylsilyl)amide (0.0.328 g, 1.65 mmole) was added and the reaction mixture was stirred at room temperature for 24 hours. Volatile components were removed under reduced pressure, and the residue was washed with 2x25 mL of hexane. Volitle components were removed under reduced pressure to yieid 0.3Q2 g {64 percent) of the orange solid dipotassium salt. A portion of this solid (0.100 g, 0.14 mmole) was dissolved in 15 mL of toluene. While stirring at room temperature, (1,4-diphenyl-1,3-butadtene)bis(triethylphosphine)zirconium dichloride (0.084 gt 0.14

mmole) 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 of the filtrate was removed under reduced pressure to give 0.115 g (88 percent) of crude product which existed as a rac/meso mixture. Further purification was carried out by recrystallization from hexanes to yield 0.015g (12percent) of rac-product as a dark red solid.
"H NMR (C6D6): 5 7.6-6.7, (mm, 26 H); 5.55 (s, 2H); 4.05-3.9O(m, 2H); 3.5 (dd, 2H); 2.7-2.4 (m, 2H); 1.78 (S.6H); 1.55(dd, 2H); 1.25 (m, 12 H); 0.95 (m, 12H).
Example 16 rac-dimethylamidoborane-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium Η4-1,4-diphenyl-1,3-butadiene

16A) Preparation of Dimethylamidodibromoborane
B(NMe2)3 was added to BBr3 dropwise. The reaction was immediate and exothermic. This mixture was allowed to stir for 2 hours at which time NMR analysis showed the reaction to be essentially quantitative and complete (22.510 g. 99.9 percent yield).
"H NMR (C6D6): 5 2.31 (6 H). ,3C NMR (C6D6): 5 41.45. 16B) Preparation of Dimethylamido-bis(2-methyl-4-phenylindinyl)borane.
A solution of dimethyamidodibromoborane (0.511 g, 2.38 mmol) in toluene (10 ml) was cooled to 0°C and diethylether (2 equivelents) 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 for overnight at room temperature. After the reaction period the volatile components were removed and the residue 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 dried under vacuum. The residue was then slurried in hexane and filtered and the orange microcrystalline solid dried under vacuum (1.246 g, >100 percent yield due to residual solvent still present as observed by NMR).
16D) Preparation of rac-[Dimethylamido-bis(2-methyl-4-phenylindene)borane]-zirconium (trans,trans-1,4-diphenyl-1,3-butadiene).
Dimcthylamido-bis(2-methy!-4-pheny-lindeny!)borane, dipotassium salt (1.246 g, 2.30 mmol) was added slowly as a solid to a solution of (1,4-diphenylbutadiene)ZrCI2(PEt3)2 (1.391, 2.30 mmol) in toluene (75 ml) and allowed to stir overnight. After the reaction period the mixture was filtered and the volatiles removed resulting in the isolation of a dark residue. This residue was slurried in hexane and filtered. Red crystals grew over a 2-hour period of time from the sitting hexane filtrate (0.222 g). The solid on the frit was washed through the frit using toluene and a second crop of crystals was grown from this mixture by allowing the solution to slowly concentrate over a period of one week by slow evaporation of the toluene (0.100 g). Combining the crystals obtained resulted in the isolation of a total of 0.322 g (18.4 percent yield) of highly pure product.
"H NMR (C6D6): 5 1.71 (s, 3 H), 1.7-1.8 (m, 2 H), 2.89 (s, 3 H), 3.4-3.5 (m, 2 H), 5.52 (s, 2 H), 6.76 (d, 3^H= 7.2 Hz, 4 H), 6.8-7.4 (m, 12 H), 7.43 (d, 3JHH= 8.4 Hz. 2 H). 13C NMR (C6D6): 5 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 (M-H)\ calcd. (M-H)+759.2610.
Example 17 bis(trimethylsilyl)amido(Ti-fluoren-9-yl)(Ti-cyclopentadienyl)borane-
zirconium dichloride.
17A) Preparation of bistrimethylsilylamido(9-fluorenyl)boron chloride
n-Butyllithium (2.5 M 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 h to give a red solution. The solution was cooled to -78 °C and added dropwise to a solution of bis(trimethylsilyl)amidoboron dichloride (TMS)2NBCI2 (2.42 g, 10.00 mmol) in THF (25 ml) at -78 °C to give a light yellow solution. The solution was stirred overnight at room temperature. Volatile components were removed, and the residue was extracted with pentane and filtered. The pentane was removed to give the desired product (3.70 g, 100 percent yield) as a white solid.

"H NMR (400 MHz. CDCI3): 5 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(l00MHz, CDCI3)S4.6. 121.0. 125.4. 127.2, 127.3. 143.0, 145.9. "B NMR (115.5 MHz, CDCI3.) 5 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 bistrimethylsilyarnido(9-fluorenyl)boron chloride (0.89 g, 2.40 mmol) THF (15 ml) at -78 °C. The resulting yellow solution was slowly warmed to room temperature with stirring and stirred over night. Volatile components 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.
"H NMR (400MHz.C6D6): 5 0.20 (s. 18 H), 1.71 (t. 2H, J = 1.4 Hz). 4.33 (s. 1 H), 5.93 (m. 1 H), 6.13 (m, 1 H), 6.69 (dd. 1 H, J = 14. 1.5 Hz), 7.09 (dt, 2H. J = 7.2, 1.5 Hz), 7. 19 (dt. 2 H, 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,) 6 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) 8 51.6. HRMS (El) calculated for C23H29BNSi, (M-CH3), 386.1932; found. 386.1945. 17C)) bis(trimethylsilyl)amidoborane(η-cyclopentadienyl)(T|-fluoren-9-yl)zirconium dichloride
A solution of lithium diisopropylamide (prepared in situ from iPr2NH (0.54 ml, 3.84 mmol) and BuU (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 slowly warmed to room temperature and stirred overnight to give a dark red solution. Volatile components were removed to give 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 oC. The mixture was warmed to room temperature and stirred overnight to give a dark red suspension. 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) to give the product as red solid.
mp = 252 - 254 (dec). "H NMR (400 MHz, CDCI3): 5 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, CDCI3)

5 4.8.5.9. 105.3. 121.4, 122.9. 124.4, 125.4, 125.7, 129.1. 143,0. nB NMR (115.5 MHz, CDCI3) δ 48.2. HRMS (El) calculated for C24H3oBNSi2Cl2Zr: 559.0434; found, 559.0443.
Example 18 diisopropylamidoborane(η-cyclopentadienyl)(ri-fluoren-9-yl)zirconium
dichloride.
18A) Preparation of Diisopropylamido(9-fluorenyl)boron chloride
The reaction conditions of Example 17A) were substantially repeated excepting that diisopropylamidodichloroboron was used in place of bis(trimethylsilyl)amido-dichloroboron. At the end of the reaction, solvent was removed, residue was extracted with CH2CI2 and filtered. Volatile components were removed to give the product (0.91 g, 98 percent) as a yellowish solid.
1H NMR (400 MHz, CDCI3): 5 1.36 (br. 6H), 1.79 (br, 6H), 4.41 (br, 1H), 7.35 (t, 2H, J = 7.7 Hz). 7.42 (t, 2H, J = 7.5 Hz). 7.50 (br, d, 2H, J = 4.7 Hz), 7.88 (d. 2H, J = 7.3 Hz). 13C NMR (100 MHz, CDCI3) 5 24.5 (br), 43.2 (br), 48.5 (br), 120.2, 124.4, 126.4, 126.9, 141.1 (br), 146.9. nB NMR (115.5 MHz, CDC13) 5 37.2. HRMS (El) Calculated for C19H23BNC!, 311.1612; found, 311.1613. 18B) Diisopropylamido(cyclopentadienyl)(9-fluorenyl)borane
The reaction conditions of Example 17 B were substantially repeated excepting that diisopropylamido(9-fluorenyl)boron was used in place of bis(trimethylsilyl)amido(9-fluorenyl)boron chloride. 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 flittered. Volatiies were removed to give the product (2.11 g, 62 percent) as a yellow solid.
HRMS (El), Calculated for C24H28BN, 341.2315. found, 341.2329. 18C) Preparation of diisopropylamidoborane(Ti~cyclopentadienyl)(T\-fluoren-9-yl)zirconium dichloride.
The reaction conditions of Example 17C) were substantially repeated excepting that diisopropylamido(9-fluorenyl)boron (1,39 g, 4.08 mmol) was used in place of bis(trirnethylsilyl)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 to give the product (0.75 g, 36 percent yield) as a red solid.
mp = 280 - 282 °C. "H NMR (500 MHz. C6D6): 51.01 (d, 6H, J = 6.6 Hz), 1.22 (d, 6H.J = 6.9 Hz), 3.67 (pent. IH. J = 6.6 Hz), 3.80 (pent, 1H. J = 6.6 Hz). 5.30 (t, 2H.

J = 2.4 Hz). 6.33 (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). ,3C NNIR (90 MHz, CDC13) 5 24.2, 25.4, 49.1. 49.8, 106.9, 122.2. 123.2, 125.4, 125.8, 129.0, 147.9, 157. 1. UB NMR (115.5 MHz, C6D6) 8 39.4. EA, calculated for C24H28BNZrCI2: C. 57.25, H, 5.57, N, 2.78. Found: C, 55.44; H, 5.30; N. 2.62.
Example 19 bis(trimethylsilyl)amidoborane bis(η-inden-1-yl)zirconium bis(dimethylamide)
Bis(trimethylsilyl)amidoboronbis(inden-1-yl) was prepared by reacting 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.
"H NMR (400 MHz, C6D6, major isomer): 8 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). "B NMR (115.5 MHz, C6D6) 8 56.8. HRMS (El) calculated for C24H32BNSi2, 401.2166; found, 401.2182. EA, Calculated for C24H32BNSi2, C, 71.82; H. 7.98; N, 3.49. Found: C, 70.06; H, 8.06; N, 3.36.
The bis(trimethylsilyl)amidoboron bis(inden-l-yl) (0.27 g, 0.67 mmol) and Zr(NMe2)4 (0.18 g, 0.67 mmol) were then combined in toluene (10 ml) 2 hours at 65°C to give a red solution. Volatile components were removed under reduced pressure to afford the product as a red foam.
"H NMR (400 MHz, C6D6): 8 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). ,3C NMR (100 MHz, C6D6) 8 5.6, 47.9, 105.1,111.5,122.2,122.9, 124.2.126.4, 128.5. 11B NMR (115.5 MHz. C6D6) 8 50.3. HRMS (El) calculated for C28η42BN3Si2Zr, 577.2057; found, 577.2061.
Example 20 Bis(trimethyl)silylamidobis(η-inden~1-yl)boranezirconium dichloride
Bis(trimethylsilyl)amidoboron bis(inden-l-yl) (0.45 g, 1.12 mmol) and Zr(NMe2)4 (0.30 g, 1.12 mmol) were combined in THF to give an intermediate which was not further purified. Volatile components were removed under reduced pressure and replaced with CH2CI2 (10 ml). The mixture was stirred with trimethylsilane chloride (1.42 ml, 11.20 mmol) overnight at room temperature. Volatile components were again removed under reduced pressure and the residue was extracted with CH2CI2 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.

"H NMR (500 MHz. C6D6): 6 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 solvent residue peak), 7.33 (d, 2H, J = 8.4 Hz). ,3C NMR (100 MHz, C6D6) 8 5.3, 112.8, 113.0. 123.6, 126.5, 127.1, 127.8, 132.1. 1,B NMR (115.5 MHz, C6D6) 6 48.5. HRMS (El) calculated for C24H3oBNSi2CI2Zr, 559.0434; found, 559.0432.
Example 21 Preparation of rac-diisopropylamidoborane-bis-η5- (2-isopropyl-4-phenyl indenyl)zirconium η4~1,4-diphenyl-1,3-butadiene

21 A) 2-lsopropyl-4-phenyl indene
Sodium hydride (2.1 g, 60 percent dispersion in oil) was placed in 500 ml flask under nitrogen atmosphere. Hexane (about 20 ml) was added to remove the oil, the mixture was stirred briefly. After stirring stopped the NaH was allowed to settle and the the liquids were removed by syringe. This procedure was repeated once more, 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 (100ml) was added via an addition funnel over 30 min. After addition of the malonate was complete, the solution was stirred for an additional 40 min. A THF solution (30 ml) of 2-phenylbenzyl bromide (12.5 g, 50.5 mmol) was added via addition funnel and the mixture was stirred overnight. The next morning 100 ml of 1N ammonium chloride was added. The solution was diluted with ether (200 ml) and the organic layer was washed with brine, dried over Na2SO,4. and stripped of solvent under reduced pressure. The orange red oil was used without further purification.
The crude alkylation product was dissolved in ethanol (300 ml) and water (75 ml). Potassium hydroxide (20 g) was added and the mixture was refluxed overnight. After cooling, ethanol was stripped under reduced pressure. Hexane was added and stirred for 1 hour to dissolve any undesired organic materials. The hexane was decanted and water was added (about 150 ml). The solution was made acidic (to pH 1) by adding concentrated HCI. The desired carboxylic product was extracted with

ether, dried over Na2SO4. and stripped under reduced pressure. NMR spectra of the crude product (10.74 g. 80 percent) indicated that ester hydrolysis and decarboxylation were complete. The crude product, which solidified to a tan 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 warm slowly to room temperature and stirred overnight. The solution was poured onto ice (about 100 ml) and stirred vigorously for 1 hour. The organic layer was separated, the aqueous layer was washed once with ether and the combined organic layers were washed with brine, dried over Na2S04, and stripped under reduced pressure. The crude 2-isopropyl-4-phenylindanone (10.0 g) as an orange-brown oil was used without further purification.
2-lsopropyl-4-phenylindanone (12.1 g, 48 mmol) was stirred in a mixture of THF and methanol (100 ml; 2/1) while sodium borohydride (1.5 g, 40 mmol) was added in small portions over 30 min. After stirring overnight, ice (about 50 ml) was added and the mixture was stirred for 0.5 h. The THF and MeOH were removed under reduced pressure- Ether (about 250 ml) was added, the pH was adjusted to pH 1 by the addition of aqueous HCI and the ether layer was separated. The ether was washed with saturated sodium bicarbonate solution, then brine, dried over Na2S04, and evaporated under reduced pressure. The mixture of alcohol isomers (11.0 g. 43.5 mmol. 90 percent)was obtained as a waxy tan solid. It was used without purification.
The crude mix of isomeric alcohols was dissolved in toluene (150 ml) to which p-toluene sulfonic acid (°-5 9) was added. The solution was refluxed in a flask equipped with a Dean-Stark trap for 1.5 h then cooled. Solid sodium bicarbonate was added and the mixture was stored overnight in a refrigerator. The next morning water (100 ml) was added arid the organic layer was separated, dried over Na2S04. and stripped under reduced pressure. The product. 2-isopropyl-4-phenylindene (10.4 g) was obtained as a brown oil. Analysis by GC indicated a purity of >96 area percent. This material was stored cojd under an inert atmosphere until ready for further conversion.

"H-NMR (CDCI3): 5 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 toluene solution (25 ml) of 2-isopropyl-4-pheny!indene (3.34 g, 14.25 mmol). in a glovebox filled with argon, was added n-butyl lithium (5.500 ml, 13 75 mmol). The mixture was stirred at room temperature overnight. The toluene was removed under reduced pressure. Hexano (20 ml) was added and removed under reduced pressure then added again (50 ml). The mixture was stirred for 1 h then filtered, washed with about 15 ml hexane and the filtrate dried under vacuum. The lithium indenide product (3.09 g) was obtained as an orange-brown powder. This material was stored in the glovebox until needed.
"H-NMR (d8-THF): 5 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): ppm 147.00, 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 toluene solution of N,N-diisopropylamidoboron dichloride (0.501 g, 2.75 mmole) at room temperature was added drop wise potassium (2-isopropyl-4-phenyl)indenide (1.50 g, 5.51 mmole in 20 ml 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 solvent was removed under reduced pressure to give a light yellow solid (1.57g, 99 percent). This material was further purified by column chromatography (silica gel /hexane) to yield 0.6g (38 percent) of a light yellow solid (96 percent pure by GC).
21D) rac-diisopropylamidoborane-bis-η5-(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 (0.380g, 0.660 mmole) was dissolved in 20 ml of toluene, 2.1 equivalents of potassium bis(trimethylsilyl) amide (0.276,1.38 mmole ) was added and the resulting mixture was stirred at room temperature for 24 hours. Removed volatiles 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 mmole) was redissolved in 20 ml of toluene, and (1,4-diphenyl-1,3-butadiene)bis(triethylphosphine)zirconium dichloride (0.384g, 0.635 mmole) was added. The solution was stirred for 2 h at room temperature, followed by heating at 80 9C for 6 hours. The product mixture was cooled to room temperature, filtered

through diatomaceous earth and the solvent of the filtrate was removed under reduced pressure. Further purification was carried out by recrystallization from hexane to yield 0.21 g (36 percent) of product as a dark red solid.
"H NMR (C6D6): 6 7.62(d, 2H); 7.42-6.7. (mm, 24 H); 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 Supported rac-diisopropylamidoborane-bis-η5-{2-methyl-4-phenylinden-1-yl)zirconium η54-1,4-diphenyl-1,3-butadiene
A toluene solution of methyldi(octyl)ammonium hydroxyphenyltris-(pentafluorophenyl)borate (825 μl, 0.040M, 33.0 umol, the ammonium cation being derived from a mixture of amines available commercially as methylbistallowamine) and a toluene solution of triethyl aluminum (TEA) (363μl, 0.10M, 36.3 umol) were combined and mixed for 30 seconds. The resulting solution was then added to 1.0 g of TEA-treated silica (Grace-Davison 948 silica, calcined at 2509C for 4 h, treated with 1.5 mmol TEA/g, washed with toluene and mixed hexanes and dried under reduced pressure). The mixture was shaken by hand to break-up clumps and then mechanically agitated for 5 minutes. The volatile components were then removed under reduced pressure. A toluene solution of rac-diisopropylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium η54-1,4-diphenyl-1,3-butadiene (1500 μl, 0.020M, 30.0 umol) was added. The mixture was shaken by hand to break-up clumps and then mechanically agitated for 5 minutes. The volatile components were once again removed under reduce pressure to give the supported catalyst as a blue/gray solid.
Example 23 Supported rac-dimethylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium η4-1 ,4-diphenyl-1,3-butadiene
A toluene solution of methyldi(octyl)ammonium hydroxyphenyltris(penta-f!uorophenyl)borate (578 μl. 0.040M, 23.1 umol) and a toluene solution of triethyl aluminum (254 u.l, 0.100M, 25.4 umol) 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 2509C 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 clumps and then mechanically agitated for 5 minutes. The volatile components were then removed under reduced pressure. A toluene solution of rac-dimethylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium η4-1.4-diphenyl-

1,3-butadiene (1050 μl, 0.020M, 21.0 umol) was added. The mixture was shaken by hand to break-up clumps and then mechanically agitated for 5 minutes. The volatile components were then removed under reduced pressure to give a teal blue solid.
Example 24 Supported /-ac-d!isopropy!amidoborane-bis-η5-(2methy!-4-phenyl:nden-1-yl)zirconium η4-1,4-diphenyl-1,3-butadiene
A toluene solution of methylbts(octadecyl)ammonium bis(tris(penta-fluorophenyl)aluminane)imidazolide (689 u.l, 0.0479M, 33.0 μmol, prepared according to USSN 09/251,664, filed Feb. 17. 1999) was added to 1.0 g of TEA-treated (Grace-Davison 948 silica, calcined at 250oC 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 clumps and then mechanically agitated for 5 minutes. The volatile components were then removed under reduced pressure. A toluene solution of raodiisopropylamidoborane-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium η4-1,4-diphenyl-1,3-butadiene (1500 μl, 0.020M, 30.0 μmol) was added. The mixture was shaken by hand to break-up clumps and then mechanically agitated for 5 minutes. The volatile components were then removed under reduced pressure to give a blue solid.
Example 25 Supported rac-dimethylamidoborane-bis-η5-(2-methyl-4-phenylinden-1-yl)zirconium η4*-1,4-diphenyl-1,3-butadiene
Under an argon atmosphere, a toluene solution of methylbis(octadecyl)ammonium bis(tris(pentafluorophenyl)aluminane)imidazolide (689 u.l, 0.0479M, 33.0 u.mol) was added to 1.0 g of TEA-treated (Grace-Davison 948 silica, calcined at 2509C 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 clumps and then mechanically agitated for 5 minutes. The volatile components were then removed under reduced pressure. A toluene solution of rac-dimethylamidoborane-bis-η5-(2-methyl-4-phenylinden-1 -yl)zirconium η4-1,4-diphenyl-1,3-butadiene (1500 μ, 0.020M, 30.0 μmol) was added. The mixture was shaken by hand to break-up clumps and then mechanically agitated for 5 minutes. The volatile components were then removed under reduced pressure to give a light biue solid.

Gas phase polymerization
A 2.5-L stirred, fixed bed autoclave was charged with 200 g dry NaCI containing 0.1 g of KH as a scavenger. Stirring was begun at 300 rpm. The reactor was pressurized to 0.8 MPa ethylene and heated to 72°C. 1-hexene was introduced to the reactor followed by the addition of hydrogen. In a separate vessel, 0.05 g of catalyst was mixed with an additional 0.1 g KH scavenger. The combined catalyst and scavenger were subsequently injected into the reactor,. Ethylene pressure was maintained on demand while hexene and hydrogen were fed to the reactor to maintain their respective concentrations. The temperature of the reactor was regulated by a circulating water bath. After 90 minutes the reactor was depressurized, and the salt and polymer were removed. The polymer was washed with copious quantities of distilled water to remove the salt, dried at 60°C, and then stabilized by addition of a hindered phenol antioxidant (Irganox™ 1010 from Ciba Geigy Corporation) and 133 mg of a phosphorus stabilizer. Activity values were calculated based on ethylene uptake. Results are contained in Table 1.
Table 1
hexene H2 MM1 Mw
Run Cat. (ppm) (ppm) Activity1 Deη5ity2 (dg/m) x 103 MWD l,o/t?

1 Ex.22 5000 0 122.7 0.899 2 Ex.23 5000 0 115.0 0.900 3 M 4000 500 84.1 0.905 4 U 5000 0 134.1 0.899 5 " 5000 3000 120.0 0.B9B 6 " 5000 6000 116.7 0.900
7 Ex.24 5000 6000 140.7 0.899 0.026 180 3.16 34.2
8 Ex.25 5000 6000 54.0 0.898 94 Ex.23 5000 8000 133.8 0.901 0.04 187 2.84 23.0 " g polymer/ g cat.+ cocat./ hr/ (MPa x 0.1)
2 density is determined by displacement technique using methylethylketone
3 melt index. I2. ASTM D-1238. 190 °C/2.16 Kg, i,10 ASTM D-1238, 190 °C/10 Kg
reaction run for 5 hours

WE CLAIM:
1. An olefin polymerization process comprising contacting one or more olefin monomers under gas phase polymerization at a temperature in the range 70 to 110°C and at a pressure from atmospheric to 10,000 atmospheres with a catalyst composition comprising a metal complex corresponding to the following formulas:

Formula 1 or Formula 2 wherein:
M is titanium, zirconium, or hafnium in the +4, +3, or +2 oxidation
state;
Y1 and Y2 are independently an anionic, cyclic or non-cyclic, rc-bonded
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 each occurrence is:


R1 is independently each occurrence hydrogen, a hydrocarbyl group, a tri(hydrocarbyl)silyl group, or a tri(hydrocarbyl)silylhydrocarbyl group, said R1 groups containing up to 20 atoms not counting hydrogen; R5 is R1 or N(R1)2; and
two R1 groups together or one or more R1 groups together with R5 may optionally be joined to form a ring structure.
2. The process as claimed in claim 1, wherein the metal complex corresponding to formula 1 is represented by formula 4, 5, 6, 7, 8 or 9:

wherein M, Z, T, R1 Q and j are as claimed in claim 1;
R2 is hydrogen, or a hydrocarbyl, halohydrocarbyl,
dihydrocarbylamino-hydrocarbyl, trilhydrocarbylsilyljhydrocarbyl,
Si(R3)3, N(R3)2, or OR3 group of up to 20 carbon or silicon atoms, and

optionally two adjacent R2 groups can be joined together, thereby forming a fused ring structure, especially an indenyl ligand or a substituted indenyl ligand; and
R3 is independently hydrogen, a hydorcarbyl group, a trihydrocarbylsilyl group or a trihydrocarbylsilylhydorcarbyl group, said R3 having up to 20 atoms not counting hydrogen.
A process as claimed in claim 2, wherein M is in the +4 oxidation
state, j = 2 and Q independently each occurrence is halide, hydride,
hydrocarbyl, silylhydrocarbyl, hydrocarbyloxide, or
dihydrocarbylamide, said Q having up to 20 atoms not counting hydrogen, or two Q groups together form an alkanediyl group or a conjugated C4-40 diene ligand that together with M form a metallocyclopentene.
A process as claimed in claim 2, wherein M is in the +3 oxidation state, J = 1 and Q is either 1) a monovalent anionic stabilizing ligand selected from the group consisting of alkyl, cycloalkyl, aryl, silyl, amido, phosphido, alkoxy, aryloxy, sulfido groups, and mixtures thereof, said Q being further substituted with an amine, phosphine, ether, or thioether containing substituent able to form a coordinate-covalent bond or chelating bond with M said ligand having up to 50 atoms not counting hydrogen: or 2) a C3-10 hydrocarbyl group comprising an ethylenic unsaturatlon able to form an ri3-bond with M.

5. A process as claimed in claim 2, wherein 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 n-complex with M.
6. A process as claimed in claim 3, wherein the metal complex corresponds to Formula 4a, 5a, 6a, 7a, 8a, or 9a, wherein the definitions of M, Z, R1, R2, and R3 are as claimed in claim 3:

and Q, independently each occurrence is a halide, hydrocarbyl, hydrocarbyloxy, or dihydrocarbylamide group of up to 10 atoms not counting hydrogen, or two Q groups together form a C4-20 diene ligand that together with M forms a metallocyclopentene.
7. A process as claimed in claim 4, wherein the metal complex
corresponds to Formula 4b, 5b, 6b, 7b, 8b, or 9b, wherein the
definitions of M, Z, R1, R2, and R3 are as claimed in claim 4:


and Q, each occurrence is a monovalent anionic stabilizing ligand selected from the group consisting of alkyl, cycloalkyl, aryl, and silyl groups, said group being further substituted with one or more amine, phosphine, or ether substituents able to form a coordinate-covalent bond or chelating bond with M, and said Q having up to 30 non-hydrogen atoms; or Q is a C3-10 hydrocarbyl group comprising an ethylenic unsaturation able to form an η3 bond with M.
8. A process as claimed in claim 5, wherein the metal complex corresponds to Formula 4c, 5c, 6c, 7c, 8c, or 9c, wherein the definitions of M, Z, R1, R2, and R3 are as claimed in claim 5:


and Q, each occurrence is a neutral conjugated diene, optionalty substituted with one or more tri(hydrocarbyl)silyl groups or tri(hydrocarbyl)silylhydrocarbyl groups, said Q having up to 30 atoms not counting hydrogen and forming a -complex with M.
A process as claimed in any of claims 1 to 8, wherein M is zirconium or hafnium.
A process as claimed in claim 9, wherein Z is boron.
A process as claimed in claim 1, wherein the metal complex is
dimethylamidoborane-bis(η5-cyclopentadienyl)zirconium dichloride,
dimethylamidoborane-bis(η5-inden-1 -yljzirconium dichloride,
dimethylamidoborane-bis(η5-2-methyl-4-phenylinden-1 -yljzirconium

dichloride, dimethylamidoborane-bis(η5-2-ethyl-4-phenylinden-1 -
yl)zirconium dichloride, dimethylamidoborane-bis(η5-2-isopropyl-4-
phenylinden-l-yl)zirconium dichloride, dimethylamidoborane-bis(η5-
2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-l-yl)zirconium
dichloride, dimethylamidoborane-bis(η5-3-t-butylinden-1 -yljzirconium
dichloride, diisopropylamidoborane-bis(η5-cyclopentadienyI)zirconium
dichloride, diisopropylamidoboranebisfaMnden-1 -yl)zirconium
dichloride, diisopropylamidoborane-bis(η5-2-methyl-4-phenylinden-1 -
yljzirconium dichloride, diisopropylamidoborane-bis(η5-2-ethyl-4-
phenylinden-l-yl)zirconium dichloride, diisopropylamidoborane-
bis(η5-2-isopropyl-4-phenylinden-1-yljzirconium dichloride,
diisopropylamidoborane-bis(η5-2-methyl-4-bis(3,5-
trifluoromethyljphenylinden-1 -yljzirconium dichloride,
diisopropylamidoborane-bis(η5-3-t-butylinden-1 -yljzirconium dichloride,
diphenylamidoborane-bis(η5-cyclopentadienyl)zirconium dichloride,
diphenylamidoborane-bis(η5-inden-1 -yljzirconium dichloride,
diphenylamidoborane-bis(η5-2-methyl-4-phenylinden-l-yljzirconium
dichloride, diphenylamidoborane-bis(η5-2-ethyl-4-phenylinden-1 -
yljzirconium dichloride, diphenylamidoborane-bis(η5-2-isopropyl-4-phenylinden-1-yljzirconium dichloride, diphenylamidoborane-bis(η5-2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1 -yljzirconium dichloride, diphenylamidoborane-bis(η5-3-t-butylinden-1 -yljzirconium dichloride,

dimethylamidoborane-bis(η5-cyclopentadienyl)zirconium 1,4-diphenyl-
1,3-butadiene, dimethylamidoboranebis(η5-inden-l-yljzirconium 1,4-
diphenyl-1,3-butadiene, dimethylamidoborane-bis(η5-2-methyl-4-
phenylinden-1-yljzirconium 1,4- diphenyl-l,3-butadiene,
dimethylamidoborane-bis(η5-2-ethyl-4-phenylinden-1 -yljzirconium
1,4-diphenyl-1,3-butadiene, dimethylamidoborane-bis(η5-2-isopropyl-
4-phenylinden-1 -yljzirconium 1,4-diphenyl-1,3-butadiene,
dimethylamidoborane-bis(η5-2-methyl-4-bis(3,5-
trifluoromethyljphenylinden-1 -yljzirconium 1,4-diphenyl-1,3-
butadiene, dimethylamidoborane-bis(η5-3-t-butylinden-1 -yljzirconium 1,4-diphenyl-1,3-butadiene,
diisopropylamidoborane-bis(η5-cyclopentadienyl)zirconium 1,4-
diphenyl-1,3-butadiene, diisopropylamidoboranebis(η5-inden-1 -
yljzirconium l,4-diphenyl-1.3-butadiene, diisopropylamidoborane-
bis(η5-2-methyl-4-phenylinden-1 -yljzirconium 1,4-diphenyl-1,3-
butadiene, diisopropylamidoborane-bis(η5-2-ethyl-4-phenylinden-1 -
yljzirconium l,4-diphenyl-l,3-butadiene, diisopropylamidoborane-
bis(η5-2-isopropyl-4-phenylinden-1 -yljzirconium 1,4-diphenyl-1,3-
butadiene, diisopropylamidoborane-bis(η5-2-methyl-4-bis(3,5-
trifluoromethyljphenylinden-1 -yljzirconium 1,4-diphenyl-1,3-
butadiene, diisopropylamidoborane-bis(η5-3-t-butylinden-1 -
yljzirconium 1,4-diphenyl-1,3-buladiene, diphenylamidoborane-bis(η5-
cyclopentadienyljzirconium 1,4-diphenyl-1,3-butadiene,
diphenylamidoboranebis(η5-inden-l -yljzirconium 1,4-diphenyl-1,3-

butadiene, diphenylamidoborane-bis(η5-2-methyl-4-phenylinden-1 -
yl)zirconium l,4-diphenyl-l,3-butadiene, diphenylamidoborane-
bis(η5-2-ethyl-4-phenylinden-1 -yl)zirconium 1,4-diphenyl-1,3-
butadiene, diphenylamidoborane-bis(η5-2-isopropyl-4-phenylinden-1 -yl)zirconium l,4-diphenyl-l,3-butadiene, diphenylamidoborane-bis(η5-2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-l-yl)zirconium l,4-diphenyl-l,3-butadiene, or diphenylamidoborane-bis(η5-3-t-butylinden-l-yl)zirconium l,4-diphenyl-l,3-butadiene.
12. A process as claimed in claim 1, wherein the catalyst additionally comprises a support material.
13. The process as claimed in claim 1, wherein the said process is a continuous gas phase polymerization.
14. The process as claimed in claim 13, wherein ethylene is homopolymerized, or a mixture of C2-6 olefins is copolymerized.
15. The process as claimed in any of the preceding claims, wherein the resulting polymer contains long chain branching.
Dated this 29th day of March, 2001.
[RITUSHKA NEGI]
OF REMFRY & SAGAR
ATTORNEY FOR THE APPLICANTS

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Patent Number 203728
Indian Patent Application Number IN/PCT/2001/00348/MUM
PG Journal Number 20/2007
Publication Date 18-May-2007
Grant Date 18-Oct-2006
Date of Filing 29-Mar-2001
Name of Patentee BP CHEMICALS LIMITED
Applicant Address BRITANNIC HOUSE, 1 FINSBURY CIRCUS LONDON EC2M 7BA U.K.
Inventors:
# Inventor's Name Inventor's Address
1 DAVID D. DEVORE AND DAVID R. NEITHAMER BOTH ARE U.S.A. CITIZEN 4881, EAST SHAFFER ROAD MIDLAND MICHIGAN 48642, U.S.A.
PCT International Classification Number N/A
PCT International Application Number N/A
PCT International Filing date 1999-09-08
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 60/103,511 1998-10-08 U.S.A.