CA2344170C - Bridged metal complexes - Google Patents

Bridged metal complexes Download PDF

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CA2344170C
CA2344170C CA002344170A CA2344170A CA2344170C CA 2344170 C CA2344170 C CA 2344170C CA 002344170 A CA002344170 A CA 002344170A CA 2344170 A CA2344170 A CA 2344170A CA 2344170 C CA2344170 C CA 2344170C
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bis
zirconium
butadiene
methyl
phenylinden
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CA2344170A1 (en
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Arthur J. Ashe, Iii
David D. Devore
Xinggao Fang
D. Patrick Green
Kevin A. Frazier
Jasson T. Patton
Francis J. Timmers
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Dow Chemical Co
University of Michigan
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Dow Chemical Co
University of Michigan
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00—Metallocene catalysts
    • C08F2420/08—Heteroatom bridge, i.e. Cp or analog where the bridging atom linking the two Cps or analogs is a heteroatom different from Si
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00—Metallocene catalysts
    • C08F2420/09—Cyclic bridge, i.e. Cp or analog where the bridging unit linking the two Cps or analogs is part of a cyclic group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00—Metallocene catalysts
    • C08F2420/10—Heteroatom-substituted bridge, i.e. Cp or analog where the bridge linking the two Cps or analogs is substituted by at least one group that contains a heteroatom
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00—Metallocene catalysts
    • C08F2420/12—Long bridge, i.e. Cp or analog where the bridging unit linking the two Cps or analogs is composed of at least two atoms which are not part of a cycle and which are not an ethylene bridge
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Abstract

A Group 4 transition metal complex containing a boron or aluminum bridging group containing a nitrogen containing electron donating group, especially an amido group.

Description

BRIDGED METAL COMPLEXES
This invention relates to certain bridged Group 4 transition metal complexes possessing a unique bridging structure and to olefin polymerization catalysts obtained from such complexes. In one form, this invention embodies Group 4 transition metal complexes containing a unique bridged, or divalent ligand structure having two anionic, delocalized n-bonded ligands attached thereto. In a second embodiment the invention relates to Group 4 transition metal complexes containing a unique bridged ligand containing one of the foregoing anionic, delocalized n-bonded moieties and one anionic amido or phosphido moiety. In a third embodiment the invention relates to Group 4 transition metal complexes containing a unique bridged ligand containing two anionic amido and/ or phosphido groups. In all cases the unique bridge consists of either boron or aluminum atoms which are further ligated with nitrogen containing groups. .
In AnQew. Chem. Int. Ed. Enal., 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-fluorenyldiboranes were disclosed in Chem. Ber., 127, p1901-1908, (1994). Diboranes having structure similar to those empioyed in the foregoing study were disclosed by the same researchers in Eur. J. Inora. 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 Oroanometallics, 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. Non-bridged metallocenes such as 1-t-butyl-4,4,bis(rl5-cyclopentadienyl)-2-(2,2,6,6-tetramethylpiperidino)-1-aza-2-bora-4-titana-cycfobutane are disclosed in Chem. Ber. (1987), 120(5), 863-5.
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.
Figures 1 and 2 are the crystal structures (ORTEP) of the compounds of Examples 2 and 5 respectively.

AMENDED SHEET

The present invention relates to certain bridged Group 4 transition metal complexes and to olefin polymerization catalysts obtained from such, said complexes corresponding to the following formulas:

-1 a-AMENDED SHEET

r ~
TZ
lZ/ ~ MQ I MQi Y~/

Formula 1 or Formula 2 wherein:
M is titanium, zirconium, or hafnium in the +4, +3, or +2 oxidation state;
Y' and Y2 are independently an anionic, cyclic or non-cyclic, n-bonded group, NR', PR'; NR'Z or PR'2;
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:

R; R' R' R' Ri2N- R' or R' =

R' R' R' R' is independently each occurrence hydrogen, a hydrocarbyl group, a tri(hydrocarbyt)silyl group, or a tri(hydrocarbyl)silylhydrocarbyl group, said R' groups containing up to 20 atoms not counting hydrogen;
R5 is R' or N(R')2; and two R' groups together or one or more R' groups together with R5 may optionally be joined to form a ring structure.
According to one aspect of the present invention, there is provided a Group 4 transition metal complex corresponding to one of the following formulas:
Yi /

TZ/ \MC~ TI \M~
Formula 1 or Formula 2 or a dimer thereof, wherein:
M is titanium, zirconium, or hafnium in tiie +4, +3, or +2 oxidation state;
Y' and Y2 are independently au-bonded anionic group, an-bonded cyclic group, a-x-bonded non-cyclic group or NR1, PR1, NR12 or PR'2i Z is boron or aluminum;
Q is a neutral, anionic or dianionic ligand group depending on the oxidation state of M;
is 1, 2 or 3 depending on the oxidation state of M and the electronic nature of Q;
T independently each occurrence is:

R; R1 R' Ri N tv O
R'pN- or R' N
/ l R' R' R

R' is independently each occurrence hydrogen, a hydrocarbyl group, a tri(hydrocarbyl)silyl group, or a tri(hydrocarbyl)silylhydrocarbyl group, said R' groups containing up to 20 atoms not counting hydrogen;
R5 is R' or N(R')2; and two R' groups together or one or more R' groups together with R5 may optionally be joined to form a ring structure.
According to another aspect of the present invention, there is provided a polymerization process comprising contacting one or more addition polymerizable monomers under polymerization conditions with a catalyst comprising one or more metal complexes as described herein.
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 Y' or Y2 are the neutral ligands, NR12 or PR'2, 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 may more accurately depicted by the formula R'2N=B.
Additionally, according to the present invention there are provided unique ligand structures Qf the following formulas:

-2a-=64693-5519 YrT{a Yi~R4 T-- Z~
T ---Z/ I
-Z
\Wi34 T "-VR4 Formula 1A or Forrnula 2A
wherein Z, T, R' and R5 are as defined above;

Y" and Y2' are an anionic, cyclic or non-cyclic, n-bonded group, NR', or PR';
and R4 is hydrogen or a trimethylsilyl group. Such ligand groups of Formula 1 A or 2A are readily prepared by contacting sources of the anionic groups (Y"R`)' and (Y2'R )', particularly the Grignard or alkali metal salts thereof, with the neutral compound TZY3 or (TZ)2Y32i where Y3 is a leaving group, especially halide, either as neat reagents or in an inert solvent, employing temperatures from -100 C to 150 2C.
Additionally, according to the present invention there is provided a process for preparing complexes of formula 1 and formula 2 in high racemic purity in the +2 formal oxidation state by contacting ligand structures of formula 1 A or 2A
where R4 is trimethylsiiyi, or deprotonated dianionic derivatives of ligand structures of formula 1 A
or formula 2A, with a Group 4 precursor of the forrnuia 3:

Fis Rs t,gLB
Y~ Y3 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)silyihydrocarbyl 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 reaction is desirably conducted in an inert solvent, especially an aliphatic or aromatic hydrocarbon or ether, employing temperatures ttom -100 2C to 150 2C.
This technique is similar to that disclosed in United States Patent No.
6,084,115, differing in that different starting reagents are employed.
Further according to the present invention there are provided catalyst compositions suitable for the polymerization of addition polymerizabte monomers comprising one or more metal complexes of formula 1 or 2 in combination with one or more activating cocatalysts or activated by use of an activating technique.
Finally, according to the present invention there is also provided a polymerization process comprising contacting one or more addition polymerizable monomers with a catalyst composition comprising one or more metal complexes of formula 1 or 2 in combination with one or more activating cocatalysts or activated by use of an activating technique. The polymerization is preferably performed under solution, slurry, suspension, or high pressure process conditions, and the catalyst composition or individual components thereof may be used in a heterogeneous state, that is, a supported state or in a homogeneous state as dictated by process conditions. The catalysts of the present invention can be used in combination with one or more additional catalysts of the same or different nature either simultaneously or sequentially in the same or in separate reactors.
Catalyst compositions according to the present invention possess improved catalytic efficiencies and improved thermal stability allowing for use under higher operating temperatures compared to catalysts comprising conventional metal complexes.
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 "n-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)2r 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 the electronic properties of the ZT, Y' and YZ moieties.
Preferred Group 4 transition metal complexes of the present invention which correspond to formula 1 or 2 are represented in formulas 4, 5, 6, 7, 8 and 9:
SUBSTITUTE SHEET (RULE 26) T Z R2 MQj T-Z\ MQj T-ZN /MQj R N

R
Formula 4 Formula 5 Formula 6 T- Z R2 T- Z ~ T- Zi N
( R ~ R. R2 MQj I MQj ~ MQj T
Zjt~Z R2 T- Z__ N/ T Z"". N/
R2 13 {

Formula 7 Formula 8 or Formula 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)3r 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 stnicture, 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.
Altematively, two Q groups may be joined together to form an alkanediyl group or a conjugated C4-4o 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 SUBSTITUTE SHEET (RULE 26) ligand having up to 50 atoms not counting hydrogen; or 2) a C3_,o hydrocarbyl group comprising an ethylenic unsaturation able to form an 113 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 n-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, R', R2, and R3 are as defined above:

Rz R2 Rz Rz Rz R12N- Z Rz M02 Rz NR3 z z R RizN-Z R MQ2 R1 2N-Z MQ2 R2 \ NR 3/

Formula 4a Formula 5a Formula 6a Rz Rz ~ I Rz MQ2 I ,,/ MQ2 RIzN - Z' NR
R 2N - Z R2 R12N- Z., NR~ 1 1 MQ2 ~ RzN -Z~ 3 R Rz NR
Formula 7a Formula 8a or Formula 9a wherein 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 C4.2o diene ligand coordinated to M in a metallocyclopentene fashion. Most highly preferably Q independently each occurrence is chloride or a C,_s hydrocarbyl group, or two Q groups together form a 2-methyl-1,3-butadienyl or 2,3-dimethyl-1,3-butadienyl group.
Specific examples of the above metal complexes wherein M is in the +3 oxidation state are shown below in formulas 4b-9b, wherein the definitions of M, Z, R', R2, and R3 are as defined above:

SUBSTITUTE SHEET (RULE 26) R 2N- R2 MQ I R2 NRa R2 R~2N-Z R MQ Rf2N-Z MQ

Formula 4b Formula 5b Formula 6b ~

R1 N- Z~~ R2 R12N- Z 2 R2 1 2 R2 MQ I R MQ R1N -Z' NR3 R 2N -~ l~ R2 R12N- Z, N 2 MQ
R~
~?l~- ~
RR'~( R2 R~2N -Z*--NR3 Formula 7b Formula 8b or Formula 9b wherein Q, each occurrence is a monovalent anionic stabilizing ligand selected from the group consisting of alkyl, cycloalkyl, aryl, and silyl groups which are further substituted with one or more amine, phosphine, or ether substituents able to form a coordinate-covalent bond or chelating bond with M, said Q having up to 30 non-hydrogen atoms; or Q is a C3.1o hydrocarbyl group comprising an ethylenic unsaturation able to form an rl3 bond with M. Most highly preferred examples of such Q ligands are 2-N,N-dimethylaminobenzyl, allyi, 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, R1, R2, and R3 are as defined above:

R2 ~ R2 R12N- Z R2 Ma R2 NR 3 \ R2 Ri 2N-Z R M(~ R1zN-Z MQ

Formula 4c Formula 5c Formula 6c SUBSTITUTE SHEET (RULE 26) R 2N - Z R2 Ri 2N- Z~ 3 R' N-Z R2 MQ 2 1 I MQ R'2N-Z- NR
N~ \MQ
2 R R 2N- Z, R R2 R~2N -Z"-NR s Formula 7c Formula 8c or Formula 9c wherein Q, each occurrence is a neutral conjugated diene, optionally substituted with one or more tri(hydrocarbyl)silyl groups or tri(hydrocarbyl)silythydrocarbyl groups, said Q having up to 30 atoms not counting hydrogen and forming a n-complex with M.
Most highly preferred Q groups are 1,4-diphenyl-1,3-butadiene, 1,3-pentadiene, methyl-1,3-pentadiene, 2,4-hexadiene, 1-phenyl-1,3-pentadiene, 1,4-dibenzyl-1,3-butadiene, 1,4-ditoiyl-1,3-butadiene, 1,4-bis(trimethylsilyl)-1,3-butadiene, and 1,4-dinaphthyl-1,3-butadiene.
Preferably in the foregoing formulas, R' independently each occurrence is C,.a alkyl, or phenyl more preferably methyl or isopropyl, most preferably methyl, Y' and Y2 are both inden-1 -yl, 2-alkyl-4-arylinden-1 -yi, 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 7a-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, Z
is boron and R' is C,_4 alkyl or phenyl, most preferably methyl or isopropyl.
Most highly preferred metal complexes are those of formulas 4a-c and 7a-c wherein Y' and Y2 are both inden-1-yl, 2-methyl -4-phenylinden-1 -yi, 3-isopropylinden-1 -yl, or 3-t-butylinden-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-ri5-cyclopentadienyi zirconium dichloride;
dimethylamidoborane-bis-r,5-cyclopentadienyi zirconium dimethyl;
dimethylamidoborane-bis-ri5-cyclopentadienyl zirconium bis-dimethylamide;
dimethylamidoborane-bis-rl5-cyclopentadienyl zirconium 2-methyl-1,3-butadiene;
SUBSTITUTE SHEET (RULE 26) dimethylamidoborane-bis-rl5-cyclopentadienyI zirconium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-ri5-cyclopentadienyl zirconium 2-N, N-dimethylaminobenzyl;
dimethylamidoborane-bis-,15-cyclopentadienyl zirconium allyl;
dimethylamidoborane-bis-rl5-cyclopentadienyl zirconium r14-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-ri5-cyclopentadienyI zirconium r14-2,4-hexadiene;
dimethylamidoborane-bis-rl5-cyclopentadienyI zirconium r14-1,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-cyclopentadienyi zirconium r14-1-phenyl-1,3-pentadiene;
dimethylamidoborane-bis-rl5-cyclopentadienyI zirconium r15-1,3-pentadiene;
dimethylamidoborane-bis-rls-n-butylcyclopentadienyI zirconium dichloride;
dimethylamidoborane-bis-rt5-n-butylcyclopentadienyi zirconium dimethyl;
dimethylamidoborane-bis-ri5-n-butylcyclopentadienyl zirconium bis-dimethylamide;
dimethylamidoborane-bis-ri5-n-butylcyclopentadienyl zirconium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-n-butylcyclopentadienyI zirconium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-,n5-n-butylcyclopentadienyI zirconium 2-N, N-dimethylaminobenzyl;
dimethylamidoborane-bis-rls-n-butylcyclopentadienyi zirconium allyl;
dimethylamidoborane-bis-rl5-n-butylcyclopentadienyi zirconium 71 4-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-n-butylcyclopentadienyI zirconium 714-2,4-hexadiene;
dimethylamidoborane-bis-ri5-n-butylcyclopentadienyI zirconium rt4-1,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-T,5-n-butylcyclopentadienyl zirconium 1i4-1-phenyl-1,3-pentadiene;
SUBSTITUTE SHEET (RULE 26) dimethylamidoborane-bis--n5-n-butylcyclopentadienyl zirconium 71 5-1,3-pentadiene;
dimethylamidoborane-bis-rI5-inden-1-ylzirconium dichloride;
dimethylamidoborane-bis-,n5-inden-l-ylzirconium dimethyl;
dimethylamidoborane-bis-r15-inden-1-ylzirconium bis-dimethylamide;
dimethylamidoborane-bis-rl5-inden-1-yfzirconium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-ri5-inden-l-ylzirconium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-inden-1-ylzirconium 2-N,N-dimethylaminobenzyl;
dimethylamidoborane-bis-ris-inden-1-ylzirconium allyl;
dimethylamidoborane-bis-rl5-inden-l-ylzirconium ri4-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-inden-1-ylzirconium r14-2,4-hexadiene;
dimethylamidoborane-bis-ri5-inden-1-ylzirconium T14-1,4-dinaphthyl-l,3-butadiene;
dimethylamidoborane-bis-,n5-inden-1-ylzirconium ri4-1-phenyl-1,3-pentadiene;
dimethylamidoborane-bis-r15-inden-1-ylzirconium 11 -1,3-pentadiene;
dimethylamidoborane-bis-ri5-(2-methylinden-1-yl)zirconium dichloride;
dimethylamidoborane-bis-rl5-(2-methylinden-1-yl)zirconium dimethyl;
dimethylamidoborane-bis-715-(2-methylinden-1-yl)zirconium bis-dimethylamide;
dimethyEamidoborane-bis-rl5-(2-methylinden-l-yl)zirconium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-(2-methylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-(2-methylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
dimethylamidoborane-bis-ri5-(2-methylinden-1-yl)zirconium allyl;
dimethylamidoborane-bis-rI5-(2-methylinden-l-yl)zirconium -q 4-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-(2-methylinden-l-yl)zirconium rj 4-2,4-hexadiene;
dimethytamidoborane-bis-Tl5-(2-methylinden-1-yl)zirconium r14-1,4-dinaphthyl-1,3-butadiene;
SUBSTITUTE SHEET (RULE 26) dimethylamidoborane-bis-r15-(2-methylinden-1-yl)zirconium r14-1-phenyl-1,3-pentadiene;
dimethylamidoborane-bis-rl5-(2-methylinden-1-yl)zirconium 11 4-1,3-pentadiene;
dimethylamidoborane-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium dichloride;
dimethylamidoborane-bis-rl5-(2-methyl-4-phenylinden-l-yl)zirconium dimethyl;
dimethylamidoborane-bis-rl5-(2-methyl-4-phenylinden-l-yl)zirconium bis-dimethylamide;
dimethylamidoborane-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-(2-methyl-4-phenylinden-l-yl)zirconium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-rt5-(2-methyl-4-phenylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
dimethylamidoborane-bis-rl5-(2-methyl-4-phenylinden-l-yl)zirconium allyl;
dimethylamidoborane-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium r14-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-(2-methyl-4-phenylinden-l-yl)zirconium 71 4-2,4-hexadiene;
dimethylamidoborane-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium r14-1,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium r14-1-phenyl-1,3-pentadiene;
dimethylamidoborane-bis-rl5-(2-methyl-4-phenylinden-l-yi)zirconium r14-1,3-pentadiene;

dimethylamidoborane-bis-rl5-(2-ethyl-4-phenylinden-1-yl)zirconium dichloride;
dimethylamidoborane-bis-rl5-(2-ethyl-4-phenylinden-1-yl)zirconium dimethyl;
dimethylamidoborane-bis-,n5-(2-ethyl-4-phenylinden-1-yl)zirconium bis-dimethylamide;
dimethylamidoborane-bis-rl5-(2-ethyl-4-phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-rt5-(2-ethyl-4-phenylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
SUBSTITUTE SHEET (RULE 26) dimethylamidoborane-bis-rl5-(2-ethyl-4-phenylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
dimethylamidoborane-bis-r15-(2-ethyl-4-phenylinden-l-yl)zirconium allyl;
dimethylamidoborane-bis-rl5-(2-ethyl-4-phenylinden-1-yl)zirconium r14-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-r15-(2-ethyl-4-phenylinden-l-yl)zirconium 714-2,4-hexadiene;
dimethylamidoborane-bis-rt5-(2-ethyl-4-phenylinden-1-yl)zirconium 714-1,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-(2-ethyl-4-phenylinden-1-yl)zirconium 714-1-phenyl-1,3-pentadiene;
dimethylamidoborane-bis-rl5-(2-ethyl-4-phenylinden-l-yl)zirconium rj 4-1,3-pentadiene;

dimethylamidoborane-bis-r15-(2-isopropyl-4-phenylinden-1-yl)zirconium dichloride;
dimethylamidoborane-bis-rl5-(2-isopropyl-4-phenylinden-l-yl)zirconium dimethyl;
dimethylamidoborane-bis-rt5-(2-isopropyi-4-phenylinden-1-yl)zirconium bis-dimethylamide;
dimethylamidoborane-bis-rl5-(2-isopropyl-4-phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-(2-isopropyl-4-phenylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-rt5-(2-isopropyl-4-phenylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
dimethylamidoborane-bis-rl5-(2-isopropyl-4-phenylinden-l-yl)zirconium allyl;
dimethylamidoborane-bis-n5-(2-isopropyl-4-phenylinden-l-yl)zirconium r14-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-(2-isopropyl-4-phenylinden-l-yl)zirconium r14-2,4-hexadiene;
dimethylamidoborane-bis-rls-(2-isopropyl-4-phenylinden-l-yl)zirconium r14-1,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-r15-(2-isopropyl-4-phenylinden-1-yl)zirconium 114-1-phenyl-1,3-pentadiene;
SUBSTITUTE SHEET (RULE 26) dimethylamidoborane-bis-rl5-(2-isopropyl-4-phenylinden-l-yl)zirconium r14-1,3-pentadiene;

dimethylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-l-yl)zirconium dichloride;
dimethylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-1-yl)zirconium dimethyl;
dimethylamidoborane-bis-rt5-(2-methyl-4-naphthylinden-l-yl)zirconium bis-dimethylamide;
dimethylamidoborane-bis-ri5-(2-methyl-4-naphthylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-115-(2-methyl-4-naphthylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-ri5-(2-methyl-4-naphthylinden-l-yi)zirconium 2-N,N-dimethylaminobenzyl;
dimethylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-l-yi)zirconium allyi;
dimethylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-1-yl)zirconium 1i4-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-l-yl)zirconium r14-2,4-hexadiene;
dimethylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-l-yl)zirconium ri4-1,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-ri5-(2-methyl-4-naphthylinden-l-yl)zirconium rt4-1-phenyl-1,3-pentadiene;
dimethylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-l-yl)zirconium 71 4-1,3-pentadiene;

dimethylamidoborane-bis-,q5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium dichloride;
dimethylamidoborane-bis-tl5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium dimethyl;
dimethylamidoborane-bis-rl5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium bis-dimethylamide;
dimethylamidoborane-bis-rl5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yi)zirconium 2-methyl-1,3-butadiene;
SUBSTITUTE SHEET (RULE 26) dimethylamidoborane-bis-rl5-(2-methyl-4-bis(3,5-trifluoromethyl) phenylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
dimethylamidoborane-bis-ri5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium allyl;
dimethylamidoborane-bis-ri5-(2-methyl-4-bis(3,5-trifIuoromethyl)phenylinden-1-yl)zirconium r14-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1 -yl)zirconium r14-2,4-hexadiene;
dimethylamidoborane-bis-ri5-(2-methyl-4-bis(3,5-trifluoromethyi)phenylinden-1-yf)zirconium r14-1,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-ri5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yI)zirconium r14-1-phenyl-1,3-pentadiene;
dimethylamidoborane-bis-115-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yI)zirconium 11 -1,3-pentadiene;

dimethylamidoborane-bis-rl5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-l-yl)zirconium dichloride;
dimethylamidoborane-bis-,95-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yi)zirconium dimethyl;
dimethyiamidoborane-bis-rl5-(2-ethyl-4-bis(3,5-trffluoromethyl)phenylinden-l-yl)zirconium bis-dimethylamide;
dimethylamidoborane-bis-ri5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-ri5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-ri5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-l-yI)zirconium 2-N,N-dimethylaminobenzyl;
dimethytamidoborane-bis-r15-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yi)zirconium allyl;
dimethylamidoborane-bis-T,5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium ri4-1,4-diphenyl-1,3-butadiene;
SUBSTITUTE SHEET (RULE 26) dimethyiamidoborane-bis-rl5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-l-yl)zirconium r14-2,4-hexadiene;
dimethylamidoborane-bis-rl5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yi)zirconium r14-1,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-l-yl)zirconium .q 4-l-phenyl-1,3-pentadiene;
dimethylamidoborane-bis-rl5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenytinden-1-yI)zirconium rt4-1,3-pentadiene;

dimethylamidoborane-bis-rl5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium dichloride;
dimethylamidoborane-bis-rl5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium dimethyl;
dimethylamidobo rane-bis-rl5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium bis-dimethylamide;
dimethylamidoborane-bis-rl5-(2-isopropyl-4-bis(3,5-triftuoromethyl)phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
dimethylamidobo rane-bis-rl5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenyiinden-l-yl)zirconium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
d im ethylamidoborane-bis-rl5-(2-isop ropyl-4-bis(3,5-trifluoromethyl)phenylinden-l-yl)zirconium aliyl;
dimethylamidoborane-bis-rl5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-l-yl)zirconium r14-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-,95-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-l-yl)zirconium r14-2,4-hexadiene;
dimethylamidoborane-bis-rts-(2-isop ropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium r14-1,4-dinaphthyl-l,3-butadiene;
dimethylamidoborane-bis-rl5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-l-yl)zirconium r14-1-phenyl-1,3-pentadiene;
dimethylamidoborane-bis-rl5-(2-isopropyl-4-bis(3,5-t(fluoromethyl)phenylinden-l-yl)zirconium r14-1,3-pentadiene;
SUBSTITUTE SHEET (RULE 26) dimethylamidoborane-bis-r,5-(3-isopropylinden-1-yl)zirconium dichloride;
dimethylamidoborane-bis-rl5-(3-isopropylinden-1-yl)zirconium dimethyl;
dimethylamidoborane-bis-rl5-(3-isopropylinden-1-yl)zirconium bis-dimethylamide;
dimethylamidoborane-bis-rl5-(3-isopropylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-115-(3-isopropyfinden-l-yl)zirconium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-(3-isopropylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
dimethylamidoborane-bis-rl5-(3-isopropylinden-1-yl)zirconium allyl;
dimethylamidoborane-bis-rl5-(3-isopropylinden-1-yl)zirconium r14-1,4-diphenyt-1,3-butadiene;
dimethylamidoborane-bis-ri5-(3-isopropylinden-1-yl)zirconium r14-2,4-hexadiene;
dimethylamidoborane-bis-ri5-(3-isopropylinden-1-yl)zirconium 11 4-1,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-(3-isopropylinden-l-yl)zirconium 114-1-phenyl-1,3-pentadiene;
dimethylamidoborane-bis-rl5-(3-isopropyiinden-1-yl)zirconium r14-1,3-pentadiene;

dimethylamidoborane-bis-rl5-(3-t-butylinden-l-yl)zirconium dichloride;
dimethylamidoborane-bis-rl5-(3-t-butylinden-1-yl)zirconium dimethyl;
dimethylamidoborane-bis-rt5-(3-t-butylinden-1-yl)zirconium bis-dimethylamide;
dimethytamidoborane-bis-rl5-(3-t-butylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-(3-t-butylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-,95-(3-t-butylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
dimethylamidoborane-bis-rls-(3-t-butylinden-1-yl)zirconium allyl;
dimethylamidoborane-bis-715-(3-t-butylinden-1-yl)zirconium 114-1,4-diphenyl-1,3-butadiene;
SUBSTITUTE SHEET (RULE 26) dimethylamidoborane-bis-rl5-(3-t-butylinden-1-yl)zirconium 1i4-2,4-hexadiene;
dimethylamidoborane-bis-ri5-(3-t-butylinden-1-yi)zirconium 114-1,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-ri5-(3-t-butylinden-1-yl)zirconium r14-1-phenyl-1,3-pentadiene;
dimethyiamidoborane-bis-ri5-(3-t-butylinden-1-yl)zirconium ri4-1,3-pentadiene;
diisopropylamidoborane-bis-il5-cyclopentadienylzirconium dichloride;
diisopropylamidoborane-bis-,95-cyclopentadienylzirconium dimethyl;
diisopropylamidoborane-bis-rl5-cycfopentadienylzirconium bis-dimethylamide;
diisopropylamidoborane-bis-rl5-cyclopentadienyizirconium 2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-cyclopentadienylzirconium 2,3-dimethyl-1,3-butadiene;
diisopropylamidoborane-bis-rI5-cyclopentadienylzirconium 2-N,N-dimethyfaminobenzyl;
diisopropylamidoborane-bis-,n5-cyclopentadienylzirconium allyl;
diisopropylamidoborane-bis-rl5-cyclopentadienylzirconium 'n 4-1,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-r15-cyclopentadienylzirconium r14-2,4-hexadiene;
diisopropylamidoborane-bis-rl5-cyclopentadienylzirconium r14-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-,n5-cyclopentadienylzirconium rl`-1-phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-rl5-cyclopentadienylzirconium ri5-1,3-pentadiene;
diisopropylamidoborane-bis-rl5-inden-l-ylzirconium dichloride;
diisopropylamidoborane-bis-r15=inden-l-ylzirconium dimethyl;
diisopropylamidoborane-bis-r15-inden-1-ylzirconium bis-dimethylamide;
diisopropylamidoborane-bis-,95-inden-l-ylzirconium 2-methyl-1,3-butadiene;
diisopropyiamidoborane-bis-,q5-inden-1-ylzirconium 2,3-dimethyl-1,3-butadiene;
diisopropylamidoborane-bis-,n5-inden-1-ylzirconium 2-N,N-dimethylaminobenzyl;
SUBSTITUTE SHEET (RULE 26) diisopropylamidoborane-bis-rl5-inden-1-ylzirconium allyl;
diisopropylamidoborane-bis-rl5-inden-1-yizirconium r14-1,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-inden-1-ylzirconium ,14-2,4-hexadiene;
diisopropylamidoborane-bis-rl5-inden-1-ylzirconium r14-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-inden-1-ylzirconium r14-1-phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-rl5-inden-1-ylzirconium 114-1,3-pentadiene;
diisopropylamidoborane-bis-,q5-(2-methylinden-1-yl)zirconium dichloride;
diisopropylamidoborane-bis-rl5-(2-methylinden-1-yl)zirconium dimethyl;
diisopropylamidoborane-bis-r15-(2-methylinden-1-yl)zirconium bis-dimethylamide;
diisopropylamidoborane-bis-rl5-(2-methylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-rt5-(2-methylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
diisopropyiamidoborane-bis-rl5-(2-methylinden-1-yl)zirconium 2-N, N-dimethylaminobenzyl;
diisopropylamidoborane-bis-rl5-(2-methylinden-1-yl)zirconium allyl;
diisopropylamidoborane-bis-rl5-(2-methylinden-1-yi)zirconium r14-1,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-(2-methylinden-1-yl)zirconium r14-2,4-hexadiene;
diisopropytamidoborane-bis-rl5-(2-methylinden-1-yl)zirconium 714-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-r15-(2-methyiinden-1-yl)zirconium r14-1-phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-rl5-(2-methylinden-1-yl)zirconium r14-1,3-pentadiene;

diisopropylamidoborane-bis-q5-(2-methyl-4-phenylinden-1-yl)zirconium dichloride;
SUBSTITUTE SHEET (RULE 26) diisopropylamidoborane-bis-rl5-(2-methyl-4-phenytinden-1-yl)zirconium dimethyl;
diisopropylamidoborane-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium bis-dimethylamide;
diisopropylamidoborane-bis-,n5-(2-methyl-4-phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
diisopropytamidoborane-bis-rl5-(2-methyl-4-phenylinden-l-yi)zirconium 2,3-dimethyl-1,3-butadiene;
diisopropyfamidoborane-bis-rl5-(2-methyl-4-phenytinden-l-yl)zirconium 2-N,N-dimethylaminobenzyl;
diisopropylamidoborane-bis-,q5-(2-methyl-4-phenylinden-1-yl)zirconium allyl;
diisopropylamidoborane-bis-rl5-(2-methyi-4-phenytinden-l-yi)zirconium 114-1,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-ri5-(2-methyi-4-phenytinden-1-yl)zirconium r14-2,4-hexadiene;
diisopropylamidoborane-bis-ris-(2-methyl-4-phenylinden-1-yl)zirconium r14-1,4-dinaphthyl-l,3-butadiene;
diisopropylamidoborane-bis-rt5-(2-methyl-4-phenylinden-1-yl)zirconium rt4-1-phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-rts-(2-methyl-4-phenytinden-1-yl)zirconium 71 4-1,3-pentadiene;

diisopropylamidoborane-bis-ri5-(2-methyl-4-naphthylinden-1-yl)zirconium dichloride;
diisopropylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-1-yi)zirconium dimethyl;
diisopropylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-1-yl)zirconium bis-dimethylamide;
diisopropylamidoborane-bis-ri5-(2-methyl-4-naphthylinden-l-yl)zirconium 2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-rt5-(2-methyl-4-naphthylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-1-yl)zirconium 2-N, N-dimethylaminobenzyl;
diisopropylamidoborane-bis-ri5-(2-methyl-4-naphthylinden-1-yi)zirconium allyl;
SUBSTITUTE SHEET (RULE 26) diisopropylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-l-yl)zirconium 11 4-1,4-diphenyl-1,3-butadiene;

diisopropylamidoborane-bis-tl5-(2-methyl-4-naphthylinden-1-yl)zirconium r1 4-2,4-hexadiene;

diisopropylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-1-yl)zirconium 11 4-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-l-yl)zirconium rt4-1-phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-rt5-(2-methyl-4-naphthylinden-1-yl)zirconium 114-1,3-pentadiene;

diisopropylamidoborane-bis-rl5-(2-methyl-4-(3,5-dimethylphenyl)inden-l-yI)zirconium dichloride;
diisopropylamidoborane-bis-rls-(2-methyl-(3,5-dimethylphenyl)inden-1-yl)zirconium dimethyl;
diisop ropylamidoborane-bis-rl5-(2-methyl-4-(3, 5-dimethyiphenyl)inden-l-yl)zirconium bis-dimethylamide;
diisopropylamidoborane-bis-r15-(2-methyl-4-(3,5-dimethylphenyl)inden-l-yl)zirconium 2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-(2-methyl-4-(3,5-dimethylphenyl)inden-l-yl)zirconium 2,3-dimethyl-1,3-butadiene;
diisopropyiamidoborane-bis-rl5-(2-methyi-4-(3,5-dimethylphenyl)inden-1-yI)zirconium 2-N,N-dimethyiaminobenzyl;
diisopropylamidoborane-bis-rl5-(2-methyl-4-(3,5-dimethylphenyl)inden-1-yI)zirconium allyl;
diisopropyfamidoborane-bis-rl5-(2-methyl-4-(3,5-dimethylphenyl)inden-1-yl)zirconium rl4-1,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-(2-methyl-4-(3,5-dimethylphenyl)inden-1-yl)zirconium rt -2,4-hexadiene;
diisopropylamidoborane-bis-rl5-(2-methyl-4-(3,5-dimethylphenyl)inden-l-yl)zirconium T14-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-(2-methyl-4-(3,5-dimethylphenyl)inden-1-yl)zirconium rt4-l-phenyl-1,3-pentadiene;
SUBSTITUTE SHEET (RULE 26) diisopropylamidoborane-bis-rl5-(2-methyl-4-(3,5-dimethylphenyi)inden-1-yl)zirconium r14-1,3-pentadiene;

diisopropylamidoborane-bis-rl5-(2-methyl-4-(3,5-difluoromethylphenyl)inden-l-yl)zirconium dichloride;
diisopropylamidoborane-bis-rl5-(2-methyl-4-(3,5-difluoromethylphenyl)inden-l-y1)zirconium dimethyl;
diisopropylamidoborane-bis-rl5-(2-methyl-4-(3,5-difluoromethylphenyl)inden-1-yl)zirconium bis-dimethylamide;
diisopropylamidoborane-bis-ri5-(2-methyl-4-(3,5-difluoromethylphenyl)inden-1-yl)zirconium 2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-(2-methyl-4-(3,5-difluoromethylphenyl)inden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
diisopropyiamidoborane-bis-rts-(2-methyl-4-(3,5-difluoromethylphenyl)inden-l-yI)zirconium 2-N,N-dimethylaminobenzyl;
diisopropylamidoborane-bis-rl5-(2-methyl-4-(3,5-difluoromethylphenyl)inden-l-yl)zirconium allyl;
diisopropylamidoborane-bis-ri5-(2-methyl-4-(3,5-difluoromethylphenyl)inden-l-yl)zirconium T,4-1,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-TI5-(2-methyl-4-(3,5-difluoromethylphenyl)inden-l-yl)zirconium r14-2,4-hexadiene;
diisopropylamidoborane-bis-rl5-(2-methyl-4-(3,5-difluoromethylphenyl) inden-1-yl)zirconium ri4-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-(2-methyl-4-(3,5-difluoromethylphenyl)inden-1-yl)zirconium rt4-l-phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-il5-(2-methyl-4-(3,5-difluoromethylphenyl)inden--1-yI)zirconium n4-1,3-pentadiene;

diisopropylamidoborane-bis-ri5-(2-ethyl-4-phenylinden-1-yl)zirconium dichloride;
diisopropylamidoborane-bis-rts-(2-ethyl-4-phenylinden-1-yl)zirconium dimethyl;
diisopropylamidoborane-bis-rl5-(2-ethyE-4-phenylinden-1-yl)zirconium bis-dimethylamide;
SUBSTITUTE SHEET (RULE 26) diisopropylamidoborane-bis-rl5-(2-ethyl-4-phenylinden-l-yl)zirconium 2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-rt5-(2-ethyl-4-phenylinden-l-yl)zirconium 2,3-dimethyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-(2-ethyl-4-phenylinden-1-yl)zirconium 2-N, N-dimethylaminobenzyl;
diisopropylamidoborane-bis-ri5-(2-ethyl-4-phenylinden-1-yl)zirconium allyl;
diisopropylamidoborane-bis-rl5-(2-ethyl-4-phenylinden-l-yl)zirconium 114-1,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-rt5-(2-ethyl-4-phenylinden-1-yl)zirconium 114-2,4-hexadiene;
diisopropylamidoborane-bis-r15-(2-ethyl-4-phenylinden-1-yl)zirconium ri4-1,4-dinaphthyl-l,3-butadiene;
diisopropylamidoborane-bis-rl5-(2-ethyl-4-phenylinden-1-yl)zirconium r14-1-phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-rls-(2-ethyl-4-phenylinden-1-yl)zirconium ij 4-1,3-pentadiene;

diisopropylamidoborane-bis-rl5-(2-isopropyl-4-phenylinden-l-yl)zirconium dichloride;
diisopropylamidoborane-bis-rl5-(2-isopropyl-4-phenylinden-1-yl)zirconium dimethyl;
diisopropylamidoborane-bis-rl5-(2-isopropyl-4-phenylinden-1-yl)zirconium bis-dimethylamide;
diisopropylamidoborane-bis-rl5-(2-isopropyl-4-phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-_n5-(2-isopropyl-4-phenylinden-1-yl)zirconium 2,3-dimethyl-i,3-butadiene;
diisopropylamidoborane-bis-rt5-(2-isopropyl-4-phenyfinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
diisopropylamidoborane-bis-ri5-(2-isopropyl-4-phenylinden-1-yl)zirconium allyl;
diisopropylamidoborane-bis-rt5-(2-isopropyl-4-phenylinden-1-yl)zirconium r1 4-1,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-ri5-(2-isopropyl-4-phenylinden-1-yl)zirconium rl4-2,4-hexadiene;
SUBSTITUTE SHEET (RULE 26) diisopropyfamidoborane-bis-rl5-(2-isopropyl-4-phenylinden-l-yl)zirconium r1 4-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-(2-isopropyl-4-phenylinden-1-yl)zirconium ri4-1-phenyl-1,3-pentadiene;
diisopropyiamidoborane-bis-rl5-(2-isopropyl-4-phenylinden-1-yl)zirconium rl4-1,3-pentadiene;

diisopropylamidoborane-bis-ri5-(3-isopropylinden-1-yl)zirconium dichloride;
diisopropylamidoborane-bis-rl5-(3-isopropylinden-1-yl)zirconium dimethyl;
diisopropylamidoborane-bis-,95-(3-isopropylinden-1-yf)zirconium bis-dimethylamide;
diisopropyiamidoborane-bis-rl5-(3-isopropylinden-l-yl)zirconium 2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-ri5-(3-isopropylinden-l-yl)zirconium 2,3-dimethyl-1,3-butadiene;
diisopropylamidoborane-bis-ri5-(3-isopropylinden-1-yl)zirconium 2-N, N-dimethylaminobenzyl;
diisopropylamidoborane-bis-r15-(3-isopropylinden-1-yl)zirconium allyl;
diisopropyiamidoborane-bis-ri5-(3-isopropylinden-l-yl)zirconium 114-1,4-diphenyl-1,3-butadiene;
diisopropyiamidoborane-bis-rl5-(3-isopropylinden-1-yl)zirconium 71 4-2,4-hexadiene;
diisopropylamidoborane-bis-rl5-(3-isopropylinden-l-yl)zirconium r14-1,4-dinaphthyl-l,3-butadiene;
diisopropylamidoborane-bis-rl5-(3-isopropylinden-l-yl)zirconium rJ 4-1-phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-rl5-(3-isopropylinden-1-yl)zirconium 11 4-1,3-pentadiene;

diisopropylamidoborane-bis-ri5-(3-t-butylinden-l-yl)zirconium dichloride;
diisopropylamidoborane-bis-rls-(3-t-butylinden-l-yl)zirconium dimethyl;
diisopropylamidoborane-bis-rI5-(3-t-butylinden-l-yl)zirconium bis-dimethylamide;
diisopropylamidoborane-bis-rl5-(3-t-butylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
SUBSTITUTE SHEET (RULE 26) diisopropylamidoborane-bis-rl5-(3-t-butylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
diisopropylamidoborane-bis-rt5-(3-t-butylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
diisopropylamidoborane-bis-rl5-(3-t-butylinden-1-yl)zirconium allyl;
diisopropylamidoborane-bis-rt5-(3-t-butylinden-l-yl)zirconium 11 4-1,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-(3-t-butylinden-1-yl)zirconium 71 4-2,4-hexadiene;
diisopropylamidoborane-bis-rt5-(3-t-butylinden-1-yl)zirconium r14-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-rt5-(3-t-butylinden-l-yl)zirconium 71 4-1-phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-rl5-(3-t-butylinden-1-yl)zirconium r14-1,3-pentadiene;

diphenylamidoborane-bis-,95-cyclopentadienyi zirconium dichloride;
diphenylamidoborane-bis-,l5-cyclopentadienyi zirconium dimethyl;
diphenylamidoborane-bis-rt5-cyclopentadienyI zirconium bis-dimethylamide;
diphenylamidoborane-bis-rl5-cyclopentadienyl zirconium 2-methyl-1,3-butadiene;
diphenylamidoborane-bis-rt5-cyclopentadienyl zirconium 2,3-dimethyl-1,3-butadiene;
diphenylamidoborane-bis-,q5-cyclopentadienyl zirconium 2-N,N-dimethylaminobenzyl;
diphenylamidoborane-bis-rl5-cyclopentadienyl zirconium allyl;
diphenylamidoborane-bis-il5-cyclopentadienyI zirconium rt4-1,4-diphenyl-1,3-butadiene;
diphenyfamidoborane-bis-rt5-cyclopentadienyi zirconium rt4-2,4-hexadiene;
diphenylamidoborane-bis-rl5-cyclopentadienyl zirconium r14-1,4-dinaphthyl-1,3-butadiene;
diphenylamidoborane-bis-rl5-cyclopentadienyl zirconium 714-1-phenyl-1,3-pentadiene;
diphenylamidoborane-bis-rl5-cyclopentadienyl zirconium q5-1,3-pentadiene;
SUBSTITUTE SHEET (RULE 26) diphenylamidoborane-bis-ri5-n-butylcyclopentadienyl zirconium dichioride;
diphenylamidoborane-bis-il5-n-butylcyclopentadienyi zirconium dimethyl;
diphenylamidoborane-bis-ri5-n-butylcyclopentadienyl zirconium bis-dimethylamide;
diphenytamidoborane-bis-rl5-n-butylcyclopentadienyl zirconium 2-methyl-1,3-butadiene;
diphenylamidoborane-bis-rt5-n-butylcyclopentadienyl zirconium 2,3-dimethyl-1,3-butadiene;
diphenylamidoborane-bis-rl5-n-butylcyclopentadienyl zirconium 2-N,N-dimethylam inobenzyl;
diphenylamidoborane-bis-rl5-n-butylcyclopentadienyl zirconium allyl;
diphenylamidoborane-bis-rl5-n-butylcyclopentadienyl zirconium 71 4-1,4-diphenyl-1,3-butadiene;
diphenylamidoborane-bis-rl5-n-butylcyclopentadienyl zirconium 114-2,4-hexadiene;
diphenylamidoborane-bis-rl5-n-butylcyclopentadienyl zirconium 71 4-1,4-dinaphthyl-1,3-butadiene;
diphenylamidoborane-bis-rl5-n-butylcyclopentadienyi zirconium r1 4-1-phenyl-1,3-pentadiene;
diphenylamidoborane-bis-rl5-n-butylcyclopentadienyl zirconium r15-1,3-pentadiene;

diphenylamidoborane-bis-n5-inden-1-ylzirconium dichioride;
diphenylamidoborane-bis-ri5-inden-1-ylzirconium dimethyl;
diphenylamidoborane-bis-115-inden-1-ylzirconium bis-dimethylamide;
diphenylamidoborane-bis-rl5-inden-1-ylzirconium 2-methyl-1,3-butadiene;
diphenylamidoborane-bis-rl5-inden-1-ylzirconium 2,3-dimethyl-1,3-butadiene;
diphenylamidoborane-bis-rl5-inden-1-ylzirconium 2-N,N-dimethylaminobenzyl;
diphenylamidoborane-bis-rl5-inden-l-ylzirconium allyl;
diphenylamidoborane-bis-ri5-inden-1-ylzirconium r14-1,4-diphenyl-1,3-butadiene;
diphenylamidoborane-bis-ri5-inden-l-ylzirconium r14-2,4-hexadiene;
SUBSTITUTE SHEET (RULE 26) diphenylamidoborane-bis-rl5-inden-l-ylzirconium n4-1,4-dinaphthyl-1,3-butadiene;
diphenylamidoborane-bis-rl5-inden-l-ylzirconium ~q4-1-phenyl-1,3-pentadiene;
diphenylamidoborane-bis-ri5-inden-1-ylzirconium r14-1,3-pentadiene;
diphenylamidoborane-bis-ri5-(2-methylinden-l-yl)zirconium dichloride;
diphenylamidoborane-bis-rl5-(2-methylinden-1-yl)zirconium dimethyl;
diphenylamidoborane-bis-,q5-(2-methylinden-1-yl)zirconium bis-dimethylamide;
diphenylamidoborane-bis-rl5-(2-methylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
diphenylamidoborane-bis-ri5-(2-methylinden-1-yl)zirconium 2,3-dimethyi-1,3-butadiene;
diphenylamidoborane-bis-rl5-(2-methylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
diphenyiamidoborane-bis-,q5-(2-methylinden-1-yl)zirconium allyi;
diphenylamidoborane-bis-rl5-(2-methylinden-1-yi)zirconium 71 4-1,4-diphenyl-1,3-butadiene;
diphenylamidoborane-bis-ri5-(2-methylinden-l-yl)zirconium 11 4-2,4-hexadiene;
diphenylamidoborane-bis-ri5-(2-methylinden-l-yl)zirconium 714-1,4-dinaphthyl-1,3-butadiene;
diphenylamidoborane-bis-115-(2-methylinden-1-yl)zirconium q 4-1-phenyl-1,3-pentadiene;
diphenyiamidoborane-bis-r,5-(2-methylinden-l-yl)zirconium 714-1,3-pentadiene;
diphenylamidoborane-bis-ri5-(2-methyl-4-phenylinden-1-yl)zirconium dichloride;
diphenylamidoborane-bis-rl5-(2-methyi-4-phenylinden-l-yl)zirconium dimethyl;
diphenylamidoborane-bis-ri5-(2-methyl-4-phenylinden-1-yl)zirconium bis-dimethylamide;
diphenylamidoborane-bis-ri5-(2-methyl-4-phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
diphenylamidoborane-bis-ri5-(2-methyl-4-phenylinden-l-yl)zirconium 2,3-dimethyl-1,3-butadiene;

SUBSTITUTE SHEET (RULE 26) diphenylamidoborane-bis-rt5-(2-methyl-4-phenylinden-1-yl)zirconium 2-N,N-dimethyiaminobenzyl;
diphenylamidoborane-bis-rl5-(2-methyl-4-phenyfinden-1-yi)zirconium allyl;
diphenylamidoborane-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium 11 4-1,4-diphenyl-1,3-butadiene;
diphenylamidoborane-bis-rls-(2-methyl-4-phenyfinden-l-yl)zirconium rt4-2,4-hexadiene;
diphenylamidoborane-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium 11 4-1,4-dinaphthyl-1,3-butadiene;
diphenylamidoborane-bis-rt5-(2-methyl-4-phenylinden-1-yl)zirconium r14-1-phenyl-1,3-pentadiene;
diphenylamidoborane-bis-rl5-(2-methyl-4-phenylinden-l-yl)zirconium 714-1,3-pentadiene;

diphenylamidoborane-bis-rl5-(2-ethyl-4-phenylinden-1-yl)zirconium dichloride;
diphenylamidoborane-bis-,q5-(2-ethyl-4-phenylinden-1-yl)zirconium dimethyl;
diphenylamidoborane-bis-rt5-(2-ethyl-4-phenylinden-1-yl)zirconium bis-dimethylamide;
diphenylamidoborane-bis-,ns-(2-ethyl-4-phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
diphenylamidoborane-bis-rl5-(2-ethyl-4-phenylinden-1-yi)zirconium 2,3-dimethyl-1,3-butadiene;
diphenylamidoborane-bis-rI5-(2-ethyl-4-phenylinden-l-yl)zirconium 2-N,N-dimethylaminobenzyl;
diphenylamidoborane-bis-rl5-(2-ethyl-4-phenylinden-l-yl)zirconium allyl;
diphenylamidoborane-bis-rt5-(2-ethyi-4-phenylinden-1-yl)zirconium ,q 4-1,4-diphenyl-1,3-butadiene;
diphenylamidoborane-bis-q5-(2-ethyl-4-phenylinden-1-yl)zirconium 11 4 -2,4-hexadiene;
diphenylamidoborane-bis-rl5-(2-ethyl-4-phenylinden-1-yl)zirconium rl -1,4-dinaphthyl-1,3-butadiene;
diphenylamidoborane-bis-rl5-(2-ethyl-4-phenylinden-l-yl)zirconium 114-1-phenyl-1,3-pentadiene;
diphenylamidoborane-bis-,"5-(2-ethyl-4-phenylinden-l-yl)zirconium 11 4-1,3-pentadiene;
SUBSTITUTE SHEET (RULE 26) diphenylamidoborane-bis-rl5-(2-isopropyi-4-phenylinden-1-yl)zirconium dichloride;
diphenylamidoborane-bis-rl5-(2-isopropyi-4-phenylinden-1-yl)zirconium dimethyl;
diphenyfamidoborane-bis-rt5-(2-isopropyl-4-phenylinden-1-yl)zirconium bis-dimethylamide;
diphenylamidoborane-bis-TI5-(2-isopropyl-4-phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
diphenylamidoborane-bis-rl5-(2-isopropyl-4-phenylinden-l-yl)zirconium 2,3-dimethyl-1,3-butadiene;
diphenylamidoborane-bis-rl5-(2-isopropyl-4-phenylinden-l-yi)zirconium 2-N,N-dimethylaminobenzyf;
diphenylamidoborane-bis-ri5-(2-isopropyl-4-phenylinden-l-yl)zirconium allyl;
diphenylamidoborane-bis-il5-(2-isopropyi-4-phenylinden-1-yi)zirconium 11 4-1,4-diphenyl-1,3-butadiene;
diphenylamidoborane-bis-ri5-(2-isopropyi-4-phenylinden-1-yl)zirconium 114-2,4-hexadiene;
diphenylamidoborane-bis-rl5-(2-isopropyl-4-phenylinden-1-yl)zirconium 11 4-1,4-dinaphthyl-1,3-butadiene;
diphenylamidoborane-bis-rt5-(2-isopropyl-4-phenylinden-1-yl)zirconium ri 4-1-phenyl-1,3-pentadiene;
diphenylamidoborane-bis-rl5-(2-isopropyl-4-phenylinden-l-yl)zirconium r14-1,3-pentadiene;
diphenylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-l-yl)zirconium dichloride;
diphenylamidoborane-bis-rt5-(2-methyl-4-naphthylinden-1-yl)zirconium dimethyl;
diphenylamidoborane-bis-ri5-(2-methyl-4-naphthylinden-l-yl)zirconium bis-dimethylamide;
diphenylamidoborane-bis-,q5-(2-methyl-4-naphthylinden-l-yl)zirconium 2-methyl-1,3-butadiene;
diphenylamidoborane-bis-il5-(2-methyl-4-naphthylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
SUBSTITUTE SHEET (RULE 26) diphenylamidoborane-bis-r}5-(2-methyl-4-naphthylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
diphenylamidoborane-bis-r15-(2-methyl-4-naphthylinden-l-yi)zirconium allyl;
diphenylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-1-yl)zirconium r1 4-1,4-diphenyl-1,3-butadiene;
diphenylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-1-yl)zirconium 114-2,4-hexadiene;
diphenylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-1-yl)zirconium 11 4-1,4-dinaphthyl-1,3-butadiene;
diphenylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-1-yl)zirconium r14-1-phenyl-l,3-pentadiene;
diphenylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-1-yl)zirconium rl -1,3-pentadiene;

diphenylamidoborane-bis-rt5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yI)zirconium dichloride;
diphenylamidoborane-bis-rl5-(2-methyl-4-bis(3,5-trifluoromethyl)phenyiinden-1-yl)zirconium dimethyl;
diphenylamidoborane-bis-ri5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1 -yl)zirconium bis-dimethylamide;
diphenylamidoborane-bis-rl5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
diphenylamidoborane-bis-,qs-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yI)zirconium 2,3-dimethyl-1,3-butadiene;
diphenylamidoborane-bis-rl5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yI)zirconium 2-N,N-dimethylaminobenzyl;
diphenylamidoborane-bis-rl5-(2-methyi-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium allyl;
diphenylamidoborane-bis-rl5-(2-methyl-4-bis(3,5-trifIuoromethyl)phenylinden-1 -yl)zirconium r14-1,4-diphenyl-l,3-butadiene;
diphenylamidoborane-bis-rl5-(2-methyl-4-bis(3,5-trifiuoromethyl)phenylinden-1-yI)zirconium rl4-2,4-hexadiene;
diphenyiamidoborane-bis-rl5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yI)zirconium q4-1,4-dinaphthyl-1,3-butadiene;
SUBSTITUTE SHEET (RULE 26) diphenylamidoborane-bis-rl5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yI)zirconium r14-1-phenyl-1,3-pentadiene;
diphenylamidoborane-bis-,q5-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium r14-1,3-pentadiene;
diphenylamidoborane-bis-r15-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-l-yl)zirconium dichloride;
diphenylamidoborane-bis-ri5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yI)zirconium dimethyl;
diphenylamidoborane-bis-rl5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-l-yI)zirconium bis-dimethylamide;
diphenylamidoborane-bis-rl5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-l-yI)zirconium 2-methyl-1,3-butadiene;
diphenytamidoborane-bis-rl5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
diphenylamidoborane-bis-ri5-(2-ethyl-4-bis(3,5-t(fluoromethyl)phenylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
diphenyiamidoborane-bis-95-(2-ethyl-4-bis(3,5-t(fluoromethyl)phenylinden-1-yl)zirconium allyl;
diphenylamidoborane-bis-ri5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-l-yI)zirconium 11 -1,4-diphenyl-1,3-butadiene;
diphenylamidoborane-bis-ri5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium r14-2,4-hexadiene;
diphenylamidoborane-bis-ri5-(2-ethyl-4-bis(3,5-t(fluoromethyl)phenyiinden-1-yI)zirconium r14-1,4-dinaphthyl-1,3-butadiene;
diphenylamidoborane-bis-ri5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium r14-1-phenyl-1,3-pentadiene;
diphenylamidoborane-bis-rl5-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-l-yl)zirconium r,4-1,3-pentadiene;
diphenylamidoborane-bis-r,5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium dichloride;
diphenylamidoborane-bis-ri5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium dimethyl;
SUBSTITUTE SHEET (RULE 26) diphenylamidoborane-bis-rl5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium bis-dimethylamide;
diphenylamidoborane-bis-rl5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
diphenylamidoborane-bis-r15-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
diphenylamidoborane-bis-rl5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
diphenylamidoborane-bis-rl5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium allyl;
diphenylamidoborane-bis-.q 5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium ri4-1,4-diphenyl-1,3-butadiene;
diphenylamidoborane-bis-,q5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-l-yl)zirconium r14-2,4-hexadiene;
diphenylamidoborane-bis-rl5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-l-yl)zirconium ri4-1,4-dinaphthyl-1,3-butadiene;
diphenylamidoborane-bis-ri5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium ri4-l-phenyl-1,3-pentadiene;
diphenylamidoborane-bis-rl5-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1 -yl)zirconium r14-1,3-pentadiene;

diphenylamidoborane-bis-rl5-(3-isopropylinden-1-yl)zirconium dichloride;
diphenylamidoborane-bis-ri5-(3-isopropylinden-l-yl)zirconium dimethyl;
diphenylamidoborane-bis-rl5-(3-isopropylinden-1-yl)zirconium bis-dimethylamide;
diphenylamidoborane-bis-rl5-(3-isopropylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
diphenylamidoborane-bis-ri5-(3-isopropylinden-l-yl)zirconium 2,3-dimethyl-1,3-butadiene;
diphenylamidoborane-bis-il5-(3-isopropylinden-1-yl)zirconium 2-N,N-dimethyfaminobenzyl;
diphenylamidoborane-bis-ri5-(3-isopropylinden-1-yl)zirconium allyl;
diphenylamidoborane-bis-rl5-(3-isopropylinden-1-yl)zirconium r14-1,4-diphenyl-1,3-butadiene;
SUBSTITUTE SHEET (RULE 26) diphenylamidoborane-bis-rl5-(3-isopropylinden-1-yl)zirconium r14-2,4-hexadiene;
diphenylamidoborane-bis-rt5-(3-isopropylinden-l-yl)zirconium 714-1,4-dinaphthyl-1,3-butadiene;
diphenylamidoborane-bis-rl5-(3-isopropylinden-1-yl)zirconium 114-1-phenyl-1,3-pentadiene;
diphenylamidoborane-bis-rl5-(3-isopropylinden-l-yl)zirconium 11 4-1,3-pentadiene;

diphenylamidoborane-bis-rl5-(3-t-bu.tylinden-1-yl)zirconium dichloride;
diphenylamidoborane-bis-rl5-(3-t-butylinden-l-yl)zirconium dimethyl;
diphenylamidoborane-bis-rt5-(3-t-butylinden-l-yl)zirconium bis-dimethylamide;
diphenylamidoborane-bis-rt5-(3-t-butylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
diphenylamidoborane-bis-rl5-(3-t-butylinden-l-yl)zirconium 2,3-dimethyl-1,3-butadiene;
diphenylamidoborane-bis-rl5-(3-t-butylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
diphenylamidoborane-bis-rl5-(3-t-butylinden-l-yl)zirconium allyi;
diphenylamidoborane-bis-rl5-(3-t-butylinden-l-yl)zirconium r14-1,4-diphenyl-1,3-butadiene;
diphenylamidoborane-bis-rt5-(3-t-butylinden-1-yl)zirconium 114-2,4-hexadiene;
diphenylamidoborane-bis-rI5-(3-t-butylinden-1-yl)zirconium rl`-1,4-dinaphthyl-1,3-butadiene;
diphenylamidoborane-bis-r15-(3-t-butylinden-1-yi)zirconium r14-1-phenyl-1,3-pentadiene;
diphenylamidoborane-bis-rt5-(3-t-butylinden-l-yl)zirconium 11 4-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-r15-cyclopentadienylzirconium dichloride;
bis(trimethylsilyl)amidoborane-bis-,n5-cyclopentadienylzirconium dimethyl;
bis(trimethylsilyl)amidoborane-bis-rl5-cyclopentadienylzirconium bis-dimethylamide;
bis(trimethylsilyl)amidoborane-bis-il5-cyclopentadienylzirconium 2-methyl-1,3-butadiene;
SUBSTITUTE SHEET (RULE 26) bis(trimethylsilyl)amidoborane-bis-rl5-cyclopentadienyizirconium 2,3-dimethyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rt5-cyclopentadienylzirconium 2-N,N-dimethylaminobenzyl;
bis(trimethyisilyl)amidoborane-bis-,n 5-cyclopentadienyizirconium allyl;
bis(trimethylsilyi)amidoborane-bis-rt5-cyclopentadienylzirconium ,14-1,4-diphenyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-cyclopentadienylzirconium ri4-2,4-hexadiene;
bis(trimethylsilyl)amidoborane-bis-ris-cyclopentadienylzirconium ri4-1,4-dinaphthyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-ri5-cyclopentadienyizirconium q 4-1-phenyl-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-cyclopentadienylzirconium r15-1,3-pentadiene;

bis(trimethylsilyl)amidoborane-bis-rl5-inden-l-ylzirconium dichloride;
bis(trimethylsilyl)amidoborane-bis-rt5-inden-1-ylzirconium dimethyl;
bis(trimethylsilyl)amidoborane-bis-r,5-inden-1-ylzirconium bis-dimethylamide;
bis(trimethylsilyl)amidoborane-bis-rt5-inden-1-ylzirconium 2-methyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-_q5-inden-1-ylzirconium 2,3-dimethyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-inden-1-ylzirconium 2-N, N-dimethylaminobenzyl;
bis(trimethylsilyl)amidoborane-bis-rl5-inden-l-ylzirconium allyl;
bis(trimethylsilyl)amidoborane-bis-il5-inden-1-ylzirconium r14-1,4-diphenyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-,n5-inden-1-ylzirconium 11 -2,4-hexadiene.;
bis(trimethylsilyl)amidoborane-bis-rt5-inden-l-ylzirconium r14-1,4-dinaphthyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-inden-1-ylzirconium ri4-1-phenyi-1,3-pentadiene;
bis(trimethylsilyi)amidoborane-bis-rt5-inden-1-ylzirconium r14-1,3-pentadiene;
SUBSTITUTE SHEET (RULE 26) bis(trimethylsilyl)amidoborane-bis-rl5-(2-methylinden-l-yl)zirconium dichioride;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methylinden-l-yl)zirconium dimethyl;
bis(trimethylsityl)amidoborane-bis-rl5-(2-methylinden-l-yl)zirconium bis-dimethylamide;
bis(trimethytsilyl)amidoborane-bis-rl5-(2-methylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rt5-(2-methylinden-l-yl)zirconium 2-N,N-dimethylaminobenzyt;
bis(trimethylsilyl)amidoborane-bis-rls-(2-methylinden-1-yl)zirconium allyl;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methylinden-1-yl)zirconium 714-1,4-diphenyt-1,3-butadiene;
bis(trimethytsilyl)amidoborane-bis-rl5-(2-methylinden-1-yl)zirconium r14-2,4-hexadiene;
bis(trimethylsiiyl)amidoborane-bis-rl5-(2-methylinden-1-yl)zirconium 11 4-1,4-dinaphthyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methylinden-l-yl)zirconium r14-1-phenyl-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methylinden-1-yl)zirconium r14-1,3-pentadiene;

bis(trimethylsilyl)amidoborane-bis-rl5-(2-methyl-4-phenylinden-1-yt)zirconium dichloride;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methyl-4-phenylinden-l-yl)zirconium dimethyl;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methyl-4-phenylinden-l-yl)zirconium bis-dimethylamide;
bis(trimethylsilyl)amidoborane-bis-,q5-(2-methyl-4-phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
SUBSTITUTE SHEET (RULE 26) bis(trimethylsilyl)amidoborane-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium allyl;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methyl-4-phenyfinden-1-yl)zirconium r14-1,4-diphenyl-1,3-butadiene;
bis(trimethylsilyi)amidoborane-bis-rl5-(2-methyl-4-phenyiinden-l-yl)zirconium 114-2,4-hexadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium 714-1,4-dinaphthyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium '9 4-1 -phenyl-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium 71 4-1,3-pentadiene;

bis(trimethylsilyl)amidoborane-bis-rl5-(2-methyl-4-naphthylinden-1-yl)zirconium dichloride;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methyl-4-naphthylinden-1-yl)zirconium dimethyl;
bis(trimethylsilyi)amidoborane-bis-r15-(2-methyl-4-naphthyEinden-1-yl)zirconium bis-dimethylamide;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methyl-4-naphthylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methyl-4-naphthylinden-l-yl)zirconium 2,3-dimethyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-il5-(2-methyl-4-naphthylinden-l-yl)zirconium 2-N,N-dimethylaminobenzyl;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methyl-4-naphthylinden-l-yl)zirconium allyl;
bis(trimethylsifyl)amidoborane-bis-rl5-(2-methyl-4-naphthylinden-1-yl)zirconium 71 4-1,4-diphenyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methyl-4-naphthylinden-l-yl)zirconium 114-2,4-hexadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methyl-4-naphthylinden-l-yl)zirconium r14-1,4-dinaphthyl-1,3-butadiene;
SUBSTITUTE SHEET (RULE 26) bis(trimethylsilyl)amidoborane-bis-rt5-(2-methyl-4-naphthylinden-1-yl)zirconium 71 4-1 -phenyl-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methyl-4-naphthylinden-1-yl)zirconium ri 4-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-rt5-(3-isopropylinden-1-yf)zirconium dichioride;
bis(trimethylsilyl)amidoborane-bis-rl5-(3-isopropylinden-1-yl)zirconium dimethyl;
bis(t(methylsilyl)amidoborane-bis-il5-(3-isopropylinden-1-yl)zirconium bis-dimethylamide;
bis(trimethylsilyl)amidoborane-bis-rl5-(3-isopropylinden-l-yl)zirconium 2-methyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(3-isopropylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(3-isopropylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
bis(trimethylsilyl)amidoborane-bis-rl5-(3-isopropylinden-1-yl)zirconium allyl;
bis(trimethylsilyl)amidoborane-bis-rl5-(3-isopropylinden-l-yl)zirconium 11 4-1,4-diphenyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(3-isopropylinden-1-yl)zirconium r14-2,4-hexadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(3-isopropylinden-1-yl)zirconium 114-1,4-dinaphthyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(3-isopropylinden-1-yl)zirconium 114-1-phenyl-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-,q5-(3-isopropylinden-1-yl)zirconium r14-1,3-pentadiene;

bis(trimethylsilyl)amidoborane-bis-rl5-(3-t-butylinden-1-yl)zirconium dichloride;
bis(trimethylsilyl)amidoborane-bis_n5-(3-t-butylinden-1-yl)zirconium dimethyl;
bis(trimethylsilyl)amidoborane-bis-rl5-(3-t-butylinden-1-yl)zirconium bis-dimethylamide;
SUBSTITUTE SHEET (RULE 26) bis(trimethylsilyi)amidoborane-bis-rl5-(3-t-butylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(3-t-butylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(3-t-butylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
bis(trimethylsilyl)amidoborane-bis-T,5-(3-t-butylinden-1-yl)zirconium allyl;
bis(trimethylsilyl)amidoborane-bis-rl5-(3-t-butylinden-1-yl)zirconium ri4-1,4-diphenyl-1,3-butadiene;
bis(trimethyfsilyi)amidoborane-bis-rl5-(3-t-butylinden-l-yl)zirconium r14-2,4-hexadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(3-t-butylinden-1-yl)zirconium r14-1,4-dinaphthyl-1,3-butadiene;
bis(trimethyisilyl)amidoborane-bis-rl5-(3-t-butylinden-1-yl)zirconium r14-1-phenyl-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(3-t-butylinden-1-yl)zirconium r14-1,3-pentadiene;

bis(diisopropylamido)diborane-l,2-bis-,n5-(2-methyl-4-phenylinden-1-yl)zirconium dichloride;
bis(diisopropylamido)diborane-1,2-bis-rl5-(2-methyl-4-phenylinden-l-yl)zirconium dimethyl;
bis(diisopropylamido)diborane-1,2-bis-ri5-(2-methyl-4-phenylinden-l-yl)zirconium bis-dimethylamide;
bis(diisopropylamido)diborane-1,2-bis-rl5-(2-methyl-4-phenylinden-1-yi)zirconium 2-methyl-1,3-butadiene;
bis(diisopropylamido)diborane-1,2-bis-r15-(2-methyl-4-phenylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
bis(diisopropylamido)diborane-1,2-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;
bis(diisopropylamido)diborane-1,2-bis-,15-(2-methyl-4-phenylinden-1-yl)zirconium allyl;
bis(diisopropylamido)diborane-1,2-bis-rl5-(2-methyl-4-phenylinden-1-yI)zirconium rl4-1,4-diphenyl-1,3-butadiene;
SUBSTITUTE SHEET (RULE 26) bis(diisopropylamido)diborane-1,2-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium r14-2,4-hexadiene;
bis(diisopropylamido)diborane-l,2-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium rt4-1,4-dinaphthyl-1,3-butadiene;
bis(diisopropylamido)diborane-1,2-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium 11 4-1-phenyl-1,3-pentadiene;
bis(diisopropylamido)diborane-1,2-bis-TI5-(2-methyl-4-phenylinden-1-yl)zirconium rt4-1,3-pentadiene;

dimethylamidoborane-bis-rl5-cyclopentadienyI hafnium dichloride;
dimethylamidoborane-bis-rl5-cyclopentadienyl hafnium dimethyl;
dimethylamidoborane-bis-rl5-cycfopentadienyl hafnium bis-dimethylamide;
dimethylamidoborane-bis-rl5-cyclopentadienyl hafnium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-r,5-cyclopentadienyl hafnium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-cyclopentadienyl hafnium 2-N,N-dimethylaminobenzyl;
dimethylamidoborane-bis-rl5-cyclopentadienyl hafnium allyl;
dimethylamidoborane-bis-rl5-cyclopentadienyl hafnium r14-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-rt5-cyclopentadienyl hafnium 114-2,4-hexadiene;
dimethyiamidoborane-bis-rl5-cyclopentadienyI hafnium 11 -1,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-rf5-cyclopentadienyl hafnium ,14-1-phenyl-1,3-pentadiene;
dimethylamidoborane-bis-rl5-cyclopentadienyI hafnium rt5-1,3-pentadiene;
dimethylamidoborane-bis-r15-n-butylcyclopentadienyl hafnium dichloride;
dimethylamidoborane-bis-rl5-n-butylcyclopentadienyI hafnium dimethyl;
dimethylamidoborane-bis-rl5-n-butylcyclopentadienyl hafnium bis-dimethylamide;
dimethylamidoborane-bis-il5-n-butylcyclopentadienyl hafnium 2-methyl-1,3-butadiene;
SUBSTITUTE SHEET (RULE 26) dimethylamidoborane-bis-rl5-n-butylcyclopentadienyl hafnium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-n-butylcyclopentadienyI hafnium 2-N,N-dimethylaminobenzyl;
dimethylamidoborane-bis-rl5-n-butylcyclopentadienyl hafnium allyl;
dimethylamidoborane-bis-rl5-n-butylcyclopentadienyl hafnium 114-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-n-butylcyclopentadienyl hafnium r14-2,4-hexadiene;
dimethylamidoborane-bis-r15-n-butylcyclopentadienyl hafnium 11 4-1,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-r15-n-butylcyclopentadienyl hafnium r14-1-phenyl-1,3-pentadiene;
dimethylamidoborane-bis-rt5-n-butylcyciopentadienyI hafnium r15-1,3-pentadiene;

dimethylamidoborane-bis-rl5-inden-l-ylhafnium dichloride;
dimethylamidoborane-bis-il5-inden-1-ylhafnium dimethyl;
dimethylamidoborane-bis-rf5-inden-1-ylhafnium bis-dimethylamide;
dimethylamidoborane-bis-rl5-inden-1-ylhafnium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-inden-1-ylhafnium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-,q5-inden-1-yfhafnium 2-N,N-dimethylaminobenzyl;
dimethylamidoborane-bis-rl5-inden-1-ylhafnium allyl;
dimethylamidoborane-bis-rl5-inden-l-ylhafnium r14-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-inden-1-ylhafnium rl -2,4-hexadiene;
dimethylamidoborane-bis-rl5-inden-l-ylhafnium 114-1,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-inden-1-ylhafnium rl -1-phenyl-1,3-pentadiene;
dimethylamidoborane-bis-rl5-inden-l-ylhafnium r14-1,3-pentadiene;
dimethylamidoborane-bis-r15-(2-methylinden-1-yl)hafnium dichloride;
dimethylamidoborane-bis-rl5-(2-methylinden-1-yl)hafnium dimethyl;
dimethylamidoborane-bis-rl5-(2-methylinden-1-yl)hafnium bis-dimethylamide;
SUBSTITUTE SHEET (RULE 26) dimethylamidoborane-bis-rl5-(2-methylinden-1-yl)hafnium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-rt5-(2-methylinden-1-yl)hafnium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-(2-methylinden-1-yl)hafnium 2-N, N-dimethylaminobenzyl;
dimethylamidoborane-bis-rl5-(2-methylinden-1-yl)hafnium allyl;
dimethylamidoborane-bis-ri5-(2-methyiinden-1-yl)hafnium ri4-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-ri5-(2-methylinden-1-yl)hafnium ri4-2,4-hexadiene;
dimethylamidoborane-bis-115-(2-methylinden-1-yi)hafnium r14-1,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-ri5-(2-methylinden-l-yl)hafnium ri4-1-phenyl-1,3-pentadiene;
dimethylamidoborane-bis-ri5-(2-methylinden-l-yl)hafnium r14-1,3-pentadiene;
dimethylamidoborane-bis-ri5-(2-methyl-4-phenylinden-l-yl)hafnium dichloride;
dimethylamidoborane-bis-ri5-(2-methyl-4-phenylinden-l-yl)hafnium dimethyl;
dimethytamidoborane-bis-ri5-(2-methyl-4-phenylinden-1-yi)hafnium bis-dimethylamide;
dimethylamidoborane-bis-,15-(2-methyl-4-phenylinden-l-yl)hafnium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-ri5-(2-methyl-4-phenylinden-1-yl)hafnium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-(2-methyl-4-phenylinden-l-yl)hafnium 2-N,N=
dimethylaminobenzyl;
dimethylamidoborane-bis-ri5-(2-methyl-4-phenyiinden-1-yl)hafnium allyl;
dimethylamidoborane-bis-ri5-(2-methyl-4-phenylinden-1-yl)hafnium rt4-1,4-diphenyl-l,3-butadiene;
dimethyEamidoborane-bis-rl5-(2-methyl-4-phenylinden-1-yl)hafnium q 4-2,4-hexadiene;
dimethyiamidoborane-bis-ri5-(2-methyl-4-phenylinden-1-yl)hafnium r14-1,4-dinaphthyl-1,3-butadiene;
SUBSTITUTE SHEET (RULE 26) dimethylamidoborane-bis-TI5-(2-methyl-4-phenylinden-l-yl)hafnium r14-1-phenyl-1,3-pentadiene;
dimethylamidoborane-bis-rl5-(2-methyl-4-phenylinden-l-yl)hafnium r14-1,3-pentadiene;
dimethylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-l-yl)hafnium dichloride;
dimethylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-l-yl)hafnium dimethyl;
dimethylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-l-yl)hafnium bis-dimethylamide;
dimethylamidoborane-bis-rt5-(2-methyl-4-naphthylinden-1-yl)hafnium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-1-yl)hafnium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-l-yl)hafnium 2-N,N-dimethylaminobenzyl;
dimethylamidoborane-bis-il5-(2-methyl-4-naphthylinden-1-yl)hafnium allyl;
dimethylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-l-yl)hafnium r14-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-1-yl)hafnium rt4-2,4-hexadiene;
dimethylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-l-yl)hafnium r14-1,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-ri5-(2-methyl-4-naphthylinden-1-yl)hafnium ri4-1-phenyl-1,3-pentadiene;
dimethylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-1-yl)hafnium r1 4-1,3-pentadiene;

dimethylamidoborane-bis-rl5-(3-isopropylinden-l-yl)hafnium dichloride;
dimethylamidoborane-bis-rl5-(3-isopropylinden-1-yl)hafnium dimethyl;
dimethylamidoborane-bis-il5-(3-isopropylinden-1-yl)hafnium bis-dimethylamide;
dimethylamidoborane-bis-ri5-(3-isopropylinden-1-yl)hafnium 2-methyl-1,3-butadiene;
SUBSTITUTE SHEET (RULE 26) dimethylamidoborane-bis-rt5-(3-isopropylinden-1-yl)hafnium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-(3-isopropylinden-1-yl)hafnium 2-N,N-dimethylaminobenzyl;
dimethylamidoborane-bis-ri5-(3-isopropylinden-1-yl)hafnium allyl;
dimethylamidoborane-bis-rt5-(3-isopropylinden-1-yl)hafnium q 4-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-ri5-(3-isopropylinden-1-yl)hafnium 11 4-2,4-hexadiene;
dimethylamidoborane-bis-rt5-(3-isopropylinden-1-yl)hafnium rj 4-1,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-(3-isopropyfinden-1-yl)hafnium 114-1-phenyl-1,3-pentadiene;
dimethylamidoborane-bis-rt5-(3-isopropylinden-1-yl)hafnium 114-1,3-pentadiene;
dimethylamidoborane-bis-,n5-(3-t-butylinden-l-yl)hafnium dichloride;
dimethylamidoborane-bis-rl5-(3-t-butylinden-1-yl)hafnium dimethyl;
dimethylamidoborane-bis-rt5-(3-t-butylinden-1-yl)hafnium bis-dimethylamide;
dimethylamidoborane-bis-r15-(3-t-butylinden-l-yl)hafnium 2-methyl-1,3-butadiene;
dimethylamidoborane-bis-rt5-(3-t-butylinden-1-yl)hafnium 2,3-dimethyl-1,3-butadiene;
dimethylamidoborane-bis-ri5-(3-t-butylinden-l-yl)hafnium 2-N,N-dimethylaminobenzyl;
dimethylamidoborane-bis-ri5-(3-t-butylinden-l-yl)hafnium allyl;
dimethytamidoborane-bis-ri5-(3-t-butylinden-1 -yi)hafnium q 4-1,4-diphenyl-1,3-butadiene;
dimethylamidoborane-bis-rt5-(3-t-butylinden-l-yl)hafnium 1i4-2,4-hexadiene;
dimethylamidoborane-bis-rl5-(3-t-butylinden-1-yl)hafnium ,14-1,4-dinaphthyl-1,3-butadiene;
dimethylamidoborane-bis-rl5-(3-t-butylinden-l-yl)hafnium 11 4-1-phenyl-1,3-pentadiene;
dimethylamidoborane-bis-115-(3-t-butylinden-l-yl)hafnium rt4-1,3-pentadiene;
SUBSTITUTE SHEET (RULE 26) diisopropylamidoborane-bis-rl5-cyclopentadienylhafnium dichloride;
diisopropylamidoborane-bis-rl5-cyclopentadienylhafnium dimethyl;
diisopropylamidoborane-bis-r15-cyclopentadienylhafnium bis-dimethylamide;
diisopropylamidoborane-bis-rl5-cyclopentadienylhafniu m 2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-T,5-cyclopentadienylhafnium 2,3-dimethyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-cyclopentadienylhafnium 2-N,N-dimethylaminobenzyl;
diisopropylamidoborane-bis-il5-cyclopentadienylhafnium allyl;
diisopropylamidoborane-bis-rl5-cyclopentadienylhafnium 11 -1,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-cyclopentadienylhafnium 71 4-2,4-hexadiene;
diisopropylamidoborane-bis-,95-cyclopentadienylhafnium q4-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-cyclopentadienylhafnium 114-1-phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-rl5-cyclopentadienylhafnium rl5-1,3-pentadiene;
diisopropylamidoborane-bis-rls-inden-1-ylhafnium dichloride;
diisopropylamidoborane-bis-r15-inden-1-ylhafnium dimethyl;
diisopropylamidoborane-bis-rl5-inden-1-ylhafnium bis-dimethylamide;
diisopropylamidoborane-bis-rI5-inden-1-ylhafnium 2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-inden-l-ylhafnium 2,3-dimethyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-inden-l-ylhafnium 2-N,N-dimethylaminobenzyl;
diisopropylamidoborane-bis-rI5-inden-l-ylhafnium allyl;
diisopropylamidoborane-bis-rl5-inden-l-ylhafnium r14-1,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-inden-l-ylhafnium r14-2,4-hexadiene;
diisopropylamidoborane-bis-rl5-inden-1-ylhafnium r14-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-rI5-inden-1-ylhafnium ,14-1-phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-rl5-inden-1-ylhafnium r14-1,3-pentadiene;
SUBSTITUTE SHEET (RULE 26) diisopropyfamidoborane-bis-rl5-(2-methylinden-1-yl)hafnium dichloride;
diisopropylamidoborane-bis-q5-(2-methyfinden-1-yl)hafnium dimethyl;
diisopropylamidoborane-bis-rI5-(2-methylinden-1 -yl)hafnium bis-dimethylamide;
diisopropylamidoborane-bis-rl5-(2-methylinden-1-yi)hafnium 2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-rt5-(2-methylinden-1-yl)hafnium 2,3-dimethyl-1,3-butadiene;
diisopropylamidoborane-bis-r15-(2-methylinden-l-yl)hafnium 2-N,N-dimethylaminobenzyl;
diisopropylamidoborane-bis-rl5-(2-methylinden-1-yl)hafnium allyl;
diisopropylamidoborane-bis-rl5-(2-methyiinden-1-yl)hafnium r14-1,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-(2-methylinden-1-yl)hafnium 714-2,4-hexadiene;
diisopropylamidoborane-bis-rl5-(2-methylinden-l-yl)hafnium 114-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-(2-methylinden-l-yl)hafnium r14-1-phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-r15-(2-methylinden-1-yl)hafnium r14-1,3-pentadiene;

diisopropylamidoborane-bis-rl5-(2-methyl-4-phenylinden-1-yl)hafnium dichloride;
diisopropylamidoborane-bis-rl5-(2-methyl-4-phenylinden-l-yl)hafnium dimethyl;
diisopropylamidoborane-bis-rl5-(2-methyl-4-phenylinden-1-yl)hafnium bis-dimethylamide;
diisopropylamidoborane-bis-rl5-(2-methyl-4-phenylinden-1-yl)hafnium 2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-rt5-(2-methyl-4-phenylinden-1-yl)hafnium 2,3-dimethyl-1,3-butadiene;
diisopropyiamidoborane-bis-r,5-(2-methyl-4-phenyiinden-1-yl)hafnium 2-N,N-dimethylaminobenzyl;
diisopropylamidoborane-bis-rl5-(2-methyl-4-phenylinden-l-yl)hafnium allyl;
SUBSTITUTE SHEET (RULE 26) diisopropylamidoborane-bis-ri5-(2-methyl-4-phenylinden-1-yl)hafnium r14-1,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-ri5-(2-methyl-4-phenylinden-1-yl)hafnium r14-2,4-hexadiene;
diisopropylamidoborane-bis-il5-(2-methyl-4-phenylinden-1-yl)hafnium 114-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-(2-methyl-4-phenylinden-1-yl)hafnium r14-1-phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-rls-(2-methyl-4-phenylinden-1-yl)hafnium r14-1,3-pentadiene;

diisopropylamidoborane-bis-ri5-(2-methyl-4-naphthylinden-1-yl)hafnium dichloride;
diisopropylamidoborane-bis-rt5-(2-methyl-4-naphthylinden-1-yl)hafnium dimethyl;
diisopropyfamidoborane-bis-rl5-(2-methyl-4-naphthylinden-l-yl)hafnium bis-dimethylamide;
diisopropylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-1-yl)hafnium 2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-l-yl)hafnium 2,3-dimethyl-1,3-butadiene;
diisopropylamidoborane-bis-r15-(2-methyl-4-naphthylinden-l-yl)hafnium 2-N,N-dimethylaminobenzyl;
diisopropylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-l-yl)hafnium allyl;
diisopropylamidoborane-bis-rl5-(2-methyl-4-naphthylinden-1-yl)hafnium ij 4-1,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-rt5-(2-methyl-4-naphthylinden-1-yl)hafnium 114-2,4-hexadiene;
diisopropylamidoborane-bis-ri5-(2-methyl-4-naphthylinden-1-yl)hafnium r14-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-rt5-(2-methyl-4-naphthylinden-1-yl)hafnium r14-1-phenyl-l,3-pentadiene;
diisopropylamidoborane-bis-rt5-(2-methyl-4-naphthylinden-l-yl)hafnium ri4-1,3-pentadiene;
SUBSTITUTE SHEET (RULE 26) diisopropylamidoborane-bis-rl5-(3-isopropylinden-1-yl)hafnium dichloride;
diisopropylamidoborane-bis-TI5-(3-isopropylinden-1-yl)hafnium dimethyl;
diisopropylamidoborane-bis-rl5-(3-isopropylinden-1-yl)hafnium bis-dimethylamide;
diisopropylamidoborane-bis-rl5-(3-isopropylinden-l-yl)hafnium 2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-(3-isopropylinden-1-yl)hafnium 2,3-dimethyl-1,3-butadiene;
diisopropylamidoborane-bis-rI5-(3-isopropylinden-l-yl)hafnium 2-N,N-dimethylaminobenzyl;
diisopropylamidoborane-bis-ri5-(3-isopropyfinden-1-yl)hafnium allyl;
diisopropylarnidoborane-bis-115-(3-isopropylinden-1-yl)hafnium r14-1,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-(3-isopropyiinden-1-yl)hafnium 114-2,4-hexadiene;
diisopropylamidoborane-bis-rl5-(3-isopropylinden-l-yl)hafnium r14-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-(3-isopropylinden-l-yl)hafnium ri4-l-phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-il5-(3-isopropylinden-1-yl)hafnium q 4-1,3-pentadiene;

diisopropylamidoborane-bis-.q5-(3-t-butylinden-1-yl)hafnium dichloride;
diisopropylamidoborane-bis-ri5-(3-t-butylinden-1-yl)hafnium dimethyl;
diisopropylamidoborane-bis-ri5-(3-t-butylinden-1-yl)hafnium bis-dimethylamide;
diisopropylamidoborane-bis-rl5-(3-t-butylinden-1-yl)hafnium 2-methyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-(3-t-butylinden-l-yl)hafnium 2,3-dimethyl-1,3-butadiene;
diisopropylamidoborane-bis-115-(3-t-butylinden-1-yl)hafnium 2-N, N-dimethylaminobenzyl;
diisopropylamidoborane-bis-r15-(3-t-butylinden-1-yl)hafnium allyl;
SUBSTITUTE SHEET (RULE 26) diisopropylamidoborane-bis-rl5-(3-t-butylinden-1-yl)hafnium r14-1,4-diphenyl-1,3-butadiene;
diisopropylamidoborane-bis-rl5-(3-t-butylinden-1-yl)hafnium ri4-2,4-hexadiene;
diisopropyiamidoborane-bis-il5-(3-t-butyfinden-l-yl)hafnium r14-1,4-dinaphthyl-1,3-butadiene;
diisopropylamidoborane-bis-rls-(3-t-butylinden-1-yl)hafnium rl -1-phenyl-1,3-pentadiene;
diisopropylamidoborane-bis-rl5-(3-t-butylinden-l-yl)hafnium r14-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-cyclopentadienylhafnium dichloride;
bis(trimethylsilyl)amidoborane-bis-r15-cyclopentadienylhafnium dimethyl;
bis(trimethylsilyl)amidoborane-bis-ri5-cyclopentadienylhafnium bis-dimethylamide;
bis(trimethylsilyl)amidoborane-bis-ri5-cyclopentadienylhafnium 2-methyl-1,3-butadiene;
bis(trimethylsilyi)amidoborane-bis-ri5-cyclopentadienylhafnium 2,3-dimethyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-ri5-cyclopentadienylhafnium 2-N, N-dimethylaminobenzyl;
bis(trimethylsilyl)amidoborane-bis-11 5-cyclopentadienylhafnium allyl;
bis(trimethylsilyl)amidoborane-bis-r,5-cyclopentadienyfhafnium 1i4-1,4-diphenyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-cyclopentadienylhafnium 11 4 -2,4-hexadiene;
bis(trimethylsilyl)amidoborane-bis-il5-cyclopentadienylhafnium r14-1,4-dinaphthyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-ri5-cyclopentadienylhafnium 11 -1-phenyl-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-ri5-cyciopentadienylhafnium r15-1,3-pentadiene;

bis(trimethylsilyl)amidoborane-bis-rl5-inden-1-ylhafnium dichioride;
bis(trimethylsilyl)amidoborane-bis-rl5-inden-1-ylhafnium dimethyl;
bis(trimethylsilyl)amidoborane-bis-ri5-inden-1-ylhafnium bis-dimethylamide;
SUBSTITUTE SHEET (RULE 26) bis(trimethylsilyl)amidoborane-bis-rl5-inden-1-ylhafnium 2-methyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-inden-1-ylhafnium 2,3-dimethyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-inden-1-ylhafnium 2-N,N-dimethyiaminobenzyl;
bis(trimethylsilyl)amidoborane-bis-rl5-inden-1-ylhafnium allyl;
bis(trimethylsilyl)amidoborane-bis-rt5-inden-1-ylhafnium 114-1,4-diphenyl-1,3-butadiene;
bis(trimethylsilyi)amidoborane-bis-rl5-inden-1-ylhafnium r14-2,4-hexadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-inden-1-ylhafnium ri4-1,4-dinaphthyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-inden-1-ylhafnium 714-1-phenyl-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-inden-1-ylhafnium 114-1,3-pentadiene;
bis(tr+methylsilyl)amidoborane-bis-rl5-(2-methylinden-1-yl)hafnium dichloride;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methylinden-1-yl)hafnium dimethyl;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methylinden-1-yl)hafnium bis-dimethylamide;
bis(trimethylsilyl)amidoborane-bis-ri5-(2-methylinden-l-yl)hafnium 2-methyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methylinden-l-yl)hafnium 2,3-dimethyl-1,3-butadiene;
bis(trimethytsilyl)amidoborane-bis-,q5-(2-methylinden-l-yl)hafnium 2-N, N-dimethylaminobenzyl;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methylinden-l-yl)hafnium allyl;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methylinden-l-yl)hafnium 114-1,4-diphenyl-1,3-butadiene;
bis(trimethytsilyl)amidoborane-bis-rl5-(2-methylinden-l-yl)hafnium q 4-2,4-hexadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methylinden-l-yl)hafnium r14-1,4-dinaphthyl-1,3-butadiene;
SUBSTITUTE SHEET (RULE 26) bis(trimethylsilyl)amidoborane-bis-,n5-(2-methylinden-l-yl)hafnium 114-1-phenyl-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-,q5-(2-methylinden-1-yl)hafnium ri4-1,3-pentadiene;
bis(trimethylsiiyl)amidoborane-bis-ri5-(2-methyl-4-phenylinden-1-yl)hafnium dichloride;
bis(trimethylsilyl)amidoborane-bis-ri5-(2-methyl-4-phenylinden-1-yl)hafnium dimethyl;
bis(trimethylsilyl)amidoborane-bis-,q5-(2-methyl-4-phenyfinden-l-yl)hafnium bis-dimethylamide;
bis(trimethylsiiyl)amidoborane-bis-ris-(2-methyl-4-phenylinden-1-yl)hafnium 2-methyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-ri5-(2-methyl-4-phenylinden-l-yl)hafnium 2,3-dimethyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-,q5-(2-methyl-4-phenylinden-1-yl)hafnium 2-N,N-dimethylaminobenzyl;
bis(trimethylsilyl)amidoborane-bis-,q5-(2-methyl-4-phenylinden-1-yl)hafnium allyl;
bis(trimethylsilyl)amidoborane-bis-ri5-(2-methyl-4-phenylinden-l-yl)hafnium ri4-1,4-diphenyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rt5-(2-methyl-4-phenylinden-1-yl)hafnium ri4-2,4-hexadiene;
bis(trimethylsilyl)amidoborane-bis-ri5-(2-methyl-4-phenylinden-1-yk)hafnium ri4-1,4-dinaphthyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rf5-(2-methyl-4-phenylinden-1-yl)hafnium ri4-1-phenyl-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-ri5-(2-methyl-4-phenylinden-1-yl)hafnium ri4-1,3-pentadiene;
bis(trimethylsily!)amidoborane-bis-ri5-(2-methyl-4-naphthylinden-1-yl)hafnium dichloride;
bis(trimethylsilyl)amidoborane-bis-ri5-(2-methyl-4-naphthylinden-1-yl)hafnium dimethyl;
SUBSTITUTE SHEET (RULE 26) bis(trimethylsilyl)amidoborane-bis-rl5-(2-methyl-4-naphthylinden-l-yl)hafnium bis-dimethylamide;
bis(trimethylsilyl)amidoborane-bis-ri5-(2-methyl-4-naphthylinden-l-yl)hafnium 2-methyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-ri5-(2-methyl-4-naphthylinden-1-yl)hafnium 2,3-dimethyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-ri5-(2-methyl-4-naphthylinden-1-yl)hafnium 2-N,N-dimethylaminobenzyl;
bis(trimethylsilyl)amidoborane-bis-r15-(2-methyl-4-naphthyiinden-l-yl)hafnium allyl;
bis(trimethylsilyl)amidoborane-bis-ri5-(2-methyl-4-naphthylinden-1-yl)hafnium 'n 4-1,4-diphenyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methyl-4-naphthylinden-1-yl)hafnium 714-2,4-hexadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methyl-4-naphthylinden-1-yl)hafnium ri 4-1,4-dinaphthyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-,n5-(2-methyl-4-naphthylinden-1-yi)hafnium 714-1-phenyl-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(2-methyl-4-naphthylinden-l-yl)hafnium q -1,3-pentadiene;

bis(trimethylsilyl)amidoborane-bis-rl5-(3-isopropylinden-l-yl)hafnium dichioride;
bis(trimethylsilyl)amidoborane-bis-rl5-(3-isopropylinden-1-yl)hafnium dimethyl;
bis(trimethylsilyl)amidoborane-bis-rl5-(3-isopropylinden-l-yl)hafnium bis-dimethylamide;
bis(trimethylsilyl)amidoborane-bis-.n5-(3-isopropylinden-1-yl)hafnium 2-methyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-ri5-(3-isopropylinden-1-yl)hafnium 2,3-dimethyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-ri5-(3-isopropylinden-1-yl)hafnium 2-N,N-dimethylaminobenzyl;
bis(trimethylsilyl)amidoborane-bis-ri5-(3-isopropylinden-1-yl)hafnium allyi;
SUBSTITUTE SHEET (RULE 26) bis(trimethylsilyl)amidoborane-bis-r15-(3-isopropyiinden-1-yl)hafnium 114-1,4-diphenyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis--q5-(3-isopropylinden-1-yl)hafnium rj 4-2,4-hexadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(3-isopropylinden-1-yl)hafnium r14-1,4-dinaphthyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(3-isopropylinden-1-yl)hafnium rl -1-phenyl-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-rls-(3-isopropylinden-1-yl)hafnium r14-1,3-pentadiene;

bis(trimethylsilyl)amidoborane-bis-rl5-(3-t-butylinden-1-yl)hafnium dichloride;
bis(trimethylsilyl)amidoborane-bis-rl5-(3-t-butylinden-1-yi)hafnium dimethyl;
bis(trimethylsilyl)amidoborane-bis-rl5-(3-t-butylinden-1-yl)hafnium bis-dimethylamide;
bis(trimethylsilyl)amidoborane-bis-rl5-(3-t-butylinden-1-yl)hafnium 2-methyi-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rls-(3-t-butylinden-1-yl)hafnium 2,3-dimethyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-115-(3-t-butylinden-1-yl)hafnium 2-N,N-dimethylaminobenzyl;
bis(trimethylsilyl)amidoborane-bis-rl5-(3-t-butylinden-1-yl)hafnium allyl;
bis(trimethylsilyi)amidoborane-bis-rl5-(3-t-butylinden-1-yl)hafnium Tj 4-1,4-diphenyl-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(3-t-butylinden-1-yl)hafnium r14-2,4-hexadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(3-t-butylinden-1-yl)hafnium 714-1,4-dinaphthyi-1,3-butadiene;
bis(trimethylsilyl)amidoborane-bis-r15-(3-t-butylinden-1-yl)hafnium 714-1-phenyl-1,3-pentadiene;
bis(trimethylsilyl)amidoborane-bis-rl5-(3-t-butylinden-1-yl)hafnium r14-1,3-pentadiene;

bis(diisopropylamido)diborane-1,2-bis-rl5-(2-methyl-4-phenylinden-1-yl)hafnium dichloride;
SUBSTITUTE SHEET (RULE 26) bis(diisopropylamido)diborane-l,2-bis-rl5-(2-methyl-4-phenylinden-l-yl)hafnium dimethyl;
bis(diisopropylamido)diborane-1,2-bis-rl5-(2-methyl-4-phenylinden-1-yl)hafnium bis-dimethylamide;
bis(diisopropylamido)diborane-1,2-bis-,q5-(2-methyl-4-phenylinden-1-yl)hafnium 2-methyl-1,3-butadiene;
bis(diisopropylamido)diborane-1,2-bis-ri5-(2-methyl-4-phenylinden-1-yl)hafnium 2,3-dimethyl-1,3-butadiene;
bis(diisopropylamido)dibo rane-1,2-bis-rl5-(2-methyl-4-phenylinden-l-yl)hafnium 2-N,N-dimethylaminobenzyl; .
bis(diisopropylamido)diborane-1,2-bis-,q5-(2-methyl-4-phenylinden-1-yI)hafnium allyl;
bis(diisopropylamido)diborane-1,2-bis-115-(2-methyl-4-phenylinden-l-yl)hafnium rt4-1,4-diphenyl-l,3-butadiene;
bis(diisopropylamido)diborane-1,2-bis-T,5-(2-methyl-4-phenylinden-1-yI)hafnium rt -2,4-hexadiene;
bis(diisopropylamido)diborane-1,2-bis-il5-(2-methyl-4-phenylinden-1-yl)hafnium 94-1,4-dinaphthyl-1,3-butadiene;
bis(diisopropylamido)diborane-1,2-bis-ri5-(2-methyl-4-phenylinden-1-yl)hafnium rt4-l-phenyl-1,3-pentadiene;
bis(diisopropylamido)diborane-1,2-bis-ri5-(2-methyl-4-phenylinden-1-yl)zirconium ,,4-1,3-pentadiene;

(r15-tetramethyicyclopentadienyl)(tert-butylamido)diisopropylamidoborane titanium dichloride;
(TI5-tetramethylcyclopentadienyl)( tert-butylamido)diisopropylamidoborane titanium dimethyl;
(rt5-tetramethylcyclopentadienyl)(tert-butylamido)diisopropylamidoborane titanium bis-dimethylamide;
(rl5-tetramethylcyclopentadienyl)(tert-butylamido)diisopropylamidoborane titanium 2-methyl-1,3-butadiene;
(rt5-tetramethylcyclopentadienyl)(tert butylamido)diisopropylamidoborane titanium 2,3-dimethyl-1,3-butadiene;
SUBSTITUTE SHEET (RULE 26) (rl5-tetramethylcyclopentadienyl)(terrt-butylamido)diisopropylamidoborane titanium 2-N,N-dimethylaminobenzyl;
(rl5-tetramethylcyclopentadienyl)(teri butyiamido)diisopropylamidoborane titanium allyl;
(rl5-tetramethylcyclopentadienyl)(tert-butylamido)diisopropylamidoborane titanium ri4-1,4-diphenyl-1,3-butadiene;
(rl5-tetramethylcyclopentadienyl)(tert butylamido)diisopropylamidoborane titanium r14-2,4-hexadiene;
(,q5-tetramethylcyclopentadienyl)(tert-butylamido)diisopropylamidoborane titanium r14-1,4-dinaphthyl-1,3-butadiene;
(r15-tetramethylcyctopentadienyl)(tert butylamido)diisopropylamidoborane titanium r14-l-phenyl-1,3-pentadiene;
(ri5-tetramethylcyclopentadienyl)(tert-butylamido)diisopropylamidoborane titanium r14-1,3-pentadiene;
(rl5-tetramethylcyclopentadienyl)(cyclohexylamido)diisopropylamidoborane titanium dichloride;
(rl5-tetramethylcyclopentadienyl)(cyclohexylamido)diisopropylamidoborane titanium dimethyl;
(rls-tetramethylcyclopentadienyl)(cyclohexylamido)diisopropytamidoborane titanium bis-dimethylamide;
(rl5-tetramethylcyclopentadienyl)(cyclohexylamido)diisopropylamidoborane titanium 2-methyl-1,3-butadiene;
(il5-tetramethylcyclopentadienyl)(cyclohexylamido)diisopropylamidoborane titanium 2,3-dimethyl-1,3-butadiene;
(rl5-tetramethylcyclopentadienyl)(cyclohexylamido)diisopropylamidoborane titanium 2-N,N-dimethylaminobenzyl;
(rt5-tetramethylcyclopentadienyl)(cyclohexylamido)diisopropylamidoborane titanium allyi;
(rls-tetramethylcyclopentadienyl)(cyclohexylamido)diisopropylamidoborane titanium r14-1,4-diphenyl-1,3-butadiene;
(r15-tetramethylcyclopentadienyl)(cyclohexylamido)diisopropylamidoborane titanium r14-2,4-hexadiene;
SUBSTITUTE SHEET (RULE 26) (r~5-tetramethylcyclopentadienyl)(cyclohexylamido)diisopropylamidoborane titanium r14-1,4-dinaphthyl-1,3-butadiene;
(r15-tetramethylcyclopentadienyl)(cyciohexylamido)diisopropylamidoborane titanium r14-1-phenyl-1,3-pentadiene;
(rt5-tetramethylcyclopentadienyl)(cyclohexylamido)diisopropylamidoborane titanium r,4-1,3-pentadiene;

(rl5-tetramethylcyclopentadienyl)(tert-butylamido) bis(diisopropylamide) diborane titanium dichioride;
(rts-tetramethyicyclopentadienyl)(tert-butylamido) bis(diisopropylamide) diborane titanium dimethyl;
(rl5-tetramethylcyclopentadienyl)(tert-butylamido) bis(diisopropylamide) diborane titanium bis-dimethylamide;
(TI5-tetramethylcyclopentadienyf)(tert-butylamido) bis(diisopropylamide) diborane titanium 2-methyl-1,3-butadiene;
(rl5-tetramethylcyclopentadienyl)(tert butyfamido) bis(diisopropylamide) diborane titanium 2,3-dimethyl-1,3-butadiene;
(ri5-tetramethylcyclopentadienyl)(tert-butylamido) bis(diisopropylamide) diborane titanium 2-N,N-dimethylaminobenzyl;
(rt5-tetramethylcyclopentadienyi)(tert-butylamido) bis(diisopropylamide) diborane titanium allyl;
(ri5-tetramethylcyclopentadienyl)(tert-butylamido) bis(diisopropylamide) diborane titanium rt4-1,4-diphenyl-1,3-butadiene;
(115-tetramethyicycfopentadienyl)(tert-butylamido) bis(diisopropylamide) diborane titanium ,14-2,4-hexadiene;
(,ts-tetramethylcyclopentadienyl)(tert-butylamido) bis(diisopropylamide) diborane titanium q -1,4-dinaphthyl-1,3-butadiene;
(rl5-tetramethylcyclopentadienyl)(tert-butylamido) bis(diisopropylamide) diborane titanium ri4-l-phenyl-1,3-pentadiene;
(r15-tetramethylcyclopentadienyl)(tert-butylamido) bis(diisopropylamide) diborane titanium r14-1,3-pentadiene;
(il5-tetramethylcyclopentadienyl)(phenylamido)diisopropylamidoborane titanium dichloride;
SUBSTITUTE SHEET (RULE 26) (rl5-tetramethylcyclopentadienyl )(phenylamido)diisopropylamidoborane titanium dimethyl;
(rl5-tetramethylcyclopentadienyl)(phenylamido)diisopropylamidoborane titanium bis-dimethylamide;
(rl5-tetramethylcyclopentadienyl)(phenylamido)diisopropylamidoborane titanium 2-methyl-1,3-butadiene;
(rl5-tetramethylcyclopentadienyl)(phenylamido)diisopropylamidoborane titanium 2,3-dimethyl-1,3-butadiene;
(rl5-tetramethyicyclopentadienyl)(phenyfamido)diisopropylamidoborane titanium 2-N,N-dimethylaminobenzyl;
(rl5-tetramethylcyclopentadienyl)(phenylamido)diisopropylamidoborane titanium allyl;
(r15-tetramethylcyclopentadienyf)(phenylamido)diisopropylamidoborane titanium ri4-1,4-diphenyl-1,3-butadiene;
(rl5-tetramethylcyclopentadienyl)(phenylamido)diisopropylamidoborane titanium r14-2,4-hexadiene;
(rl5-tetramethylcyclopentadienyl)(phenylamido)diisopropylamidoborane titanium ri4-1,4-dinaphthyl-1,3-butadiene;
(rl5-tetramethylcyclopentadienyl)(phenylamido)diisopropylamidoborane titanium r14-1-phenyl-l,3-pentadiene;
(,q5-tetramethyfcyclopentadienyl)(phenylamido)diisopropylamidoborane titanium r,4-1,3-pentadiene;

(r15-tetramethyicyclopentadienyl)(tert-butylamido) dimethylamidoborane titanium dichforide;
(rl5-tetramethylcyclopentadienyl)(tert-butylamido) dimethylamidoborane titanium dimethyl;
(ri5-tetramethylcyclopentadienyl)(tert butylamido) dimethylamidoborane titanium bis-dimethylamide;
(rl5-tetramethylcyciopentadienyl)(tert-butylamido) dimethylamidoborane titanium 2-methyl-1,3-butadiene;
(,95-tetramethytcyclopentadienyl)(tert-butylamido) dimethylamidoborane titanium 2,3-dimethyl-1,3-butadiene;
SUBSTITUTE SHEET (RULE 26) (ri5-tetramethylcyclopentadienyl)(tert-butylamido) dimethylamidoborane titanium 2-N,N-dimethylaminobenzyl;
(,q5-tetramethylcyciopentadienyi)(tert-butylamido) dimethylamidoborane titanium allyl;
(,95-tetramethylcyclopentadienyl)(tert-butylamido) dimethylamidoborane titanium r,4-1,4-diphenyl-1,3-butadiene;
(il5-tetramethylcyclopentadienyi)(tert-butylamido) dimethylamidoborane titanium ri4-2,4-hexadiene;
(,95-tetramethylcyclopentadienyl)(tert-butylamido) dimethylamidoborane titanium 11 -1,4-dinaphthyl-1,3-butadiene;
(ri5-tetramethylcyclopentadienyl)(tert-butyiamido) dimethylamidoborane titanium rt4-l-phenyl-1,3-pentadiene;
(,15-tetramethylcyclopentadienyl)(tert-butylamido) dimethylamidoborane titanium r14-1,3-pentadiene;
(rj5-inden-l-yl)(tert-butylamido)diisopropylamidoborane titanium dichloride;
(r15-inden-l-yl)( tert-butyiamido)diisopropylamidoborane titanium dimethyl;
(rl5-inden-l-yl)(tert-butylamido)diisopropylamidoborane titanium bis-dimethylamide;
(rl5-inden-l-yl)(tert-butylamido)diisopropylamidoborane titanium 2-methyl-1,3-butadiene;
(,q5-inden-1-yl)(tert-butylamido)diisopropylamidoborane titanium 2,3-dimethyl-1,3-butadiene;
(rj5-inden-l-yl)(tert-butylamido)diisopropylamidoborane titanium 2-N,N-dimethylaminobenzyl;
(ri5-inden-1-yl)(tert-butylamido)diisopropyiamidoborane titanium allyl;
(rl5-inden-l-yl)(tert butylamido)diisopropylamidoborane titanium r14-1,4-diphenyl-1,3-butadiene;
(rl5-inden-l-yl)(tert-butylamido)diisopropylamidoborane titanium r1 4-2,4-hexadiene;
(r15-inden-l-yl)(tert-butylamido)diisopropylamidoborane titanium 714-1,4-dinaphthyl-1,3-butadiene;
(r15-inden-1-yl)(tert butylamido)diisopropylamidoborane titanium ri4-1-phenyl-1,3-pentadiene;
SUBSTITUTE SHEET (RULE 26) (,q5-inden-1-yl)(tert-butylamido)diisopropylamidoborane titanium r14-1,3-pentadiene;
(,q5-2,3-dimethyl-1-)(tert-butylamido)diisopropylamidoborane titanium dichloride;
(,q5-2,3-dimethylinden-1-yi)(tert-butylamido)diisopropylamidoborane titanium dimethyl;
(rl5 -2,3-dimethylinden-l-yl)(tert-butylamido)diisopropylamidoborane titanium bis-dimethylamide;
(rl5-2,3-dimethylinden-1-yl)(tert butylamido)diisopropylamidoborane titanium 2-methyl-1,3-butadiene;
(rl5-2,3-dimethylinden-1-yl)(tert-butylamido)diisopropylamidoborane titanium 2,3-dimethyl-1,3-butadiene;
(rt5-2,3-dimethylinden-l-yl)(tert-butylamido)diisopropylamidoborane titanium 2-N,N-dimethylaminobenzyl;
(r15-2,3-dimethylinden-1-yi)(tert-butylamido)diisopropylamidoborane titanium allyl;
(rl5-2,3-dimethylinden-1-yl)(tert-butylamido)diisopropylamidoborane titanium ri 4-1,4-diphenyl-1,3-butadiene;
(,n5-2,3-dimethylinden-l-yl)(tert-butylamido)diisopropylamidoborane titanium 11 4-2,4-hexadiene;
(rt5-2,3-dimethylinden-1-yl)(tert-butylamido)diisopropylamidoborane titanium ri 4-1,4-dinaphthyl-1, 3-butadiene;
(,n5-2,3-dimethylinden-l-yl)(tert-butylamido)diisopropyiamidoborane titanium rj 4-1 -phenyl-1,3-pentadiene;
(r15-2,3-dimethylinden-l-yl)(tert butylamido)diisopropylamidoborane titanium 114-1,3-pentadiene;
(rls-2-pyrrolidenylinden-l-yl)(tert-butylamido)diisopropylamidoborane titanium dichloride;
(r15-2-pyrrolidenylinden-1-yl)(terf-butylamido)diisopropylamidoborane titanium dimethyl;
(rl5-2-pyrrolidenylinden-1-yl)(tert-butylamido)diisopropylamidoborane titanium bis-dimethylamide;
SUBSTITUTE SHEET (RULE 26) (rI5-2-pyrrolidenylinden-l-yl)(tert butylamido)diisopropylamidoborane titanium 2-methyl-1,3-butadiene;
(rls-2-pyrrolidenylinden-l-yl)(tert-butylamido)diisopropylamidoborane titanium 2,3-dimethyl-1,3-butadiene;
(ri5-2-pyrrolidenylinden-1-yl)(tert butylamido)diisopropylamidoborane titanium 2-N, N-dimethylaminobenzyl;
(r15-2-pyrrolidenylinden-l-yl)(tert-butylamido)diisopropylamidoborane titanium allyl;
(,q5-2-pyrrolidenylinden-l-yl)(tert-butylamido)diisopropylamidoborane titanium 114-1,4-diphenyl-1,3-butadiene;
(r15-2-pyrrolidenylinden-l-yl)(tert-butylamido)diisopropylamidoborane titanium r14-2,4-hexadiene;
(115-2-pyrrolidenylinden-1-yi)(tert butylamido)diisopropylamidoborane titanium 714-1,4-dinaphthyl-1,3-butadiene;
(rl5-2-pyrrolidenylinden-1 -yl)(tert butylamido)diisopropylamidoborane titanium r14-1-phenyl-l,3-pentadiene;
(r15-2-pyrrolidenylinden-l-yl)(tert-butylamido)diisopropylamidoborane titanium 11 4-1,3-pentadiene;

bis-phenylamido-bis(diisopropylamido)diborane titanium dichloride;
bis-phenylamido-bis(diisopropylamido)diborane titanium dimethyl;
bis-phenylamido-bis(diisopropylamido)diborane titanium bis-dimethylamide;
bis-phenylamido-bis(diisopropylamido)diborane titanium 2-methyl-1,3-butadiene;
bis-phenylamido-bis(diisopropylamido)diborane titanium 2,3-dimethyl-1,3-butadiene;
bis-phenylamido-bis(diisopropylamido)diborane titanium 2-N,N-dimethylaminobenzyl;
bis-phenylamido-bis(diisopropylamido)diborane titanium allyl;
bis-phenylamido-bis(diisopropylamido)diborane titanium r,4-1,4-diphenyl-1,3-butadiene;
bis-phenylamido-bis(diisopropylamido)diborane titanium rl -2,4-hexadiene;
bis-phenylamido-bis(diisopropylamido)diborane titanium 'n 4-1,4-dinaphthyl-1,3-butadiene;
SUBSTITUTE SHEET (RULE 26) bis-phenylamido-bis(diisopropyfamido)diborane titanium rt4-l-phenyl-1,3-pentadiene;
bis-phenylamido-bis(diisopropylamido)diborane titanium r14-1,3-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 r14-1,4-diphenyl-1,3-butadiene;
bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diborane titanium r14-2,4-hexadiene;
bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diborane titanium r14-1,4-dinaphthyl-1,3-butadiene;
bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diborane titanium q4-1-phenyl-1,3-pentadiene;
bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diborane titanium il 4-1,3-pentadiene;

bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titanium dichloride;
bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titanium dimethyl;
bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titanium bis-dimethylamide;
bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titanium 2-methyl-1,3-butadiene;
SUBSTITUTE SHEET (RULE 26) bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titanium 2,3-dimethyl-1,3-butadiene;
bis-3,5-dimethylbenzylamido-bis(dimethyfamido)diborane titanium 2-N,N-dimethylaminobenzyl;
bis-3,5--dimethylbenzylamido-bis(dimethylamido)diborane titanium allyi;
bis-3,5--dimethylbenzylamido-bis(dimethylamido)diborane titanium rj 4-1,4-diphenyl-1,3-butadiene;
bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titanium ri4-2,4-hexadiene;
bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titanium rt -1,4-dinaphthyl-1,3-butadiene;
bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titanium q 4-1-phenyl-1,3-pentadiene;
bis-3,5-dimethylbenzytamido-bis(dimethylamido)diborane titanium rl -1,3-pentadiene;

bis-2,6-dimethylbenzylamido-bis(dimethylamido)diborane titanium dichloride;
bis-2,6-dimethylbenzylamido-bis(dimethylamido)diborane titanium dimethyl;
bis-2,6-dimethylbenzylamido-bis(dimethylamido)diborane titanium bis-dimethylamide;
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-dimethylaminobenzyl;
bis-2,6-dimethylbenzylamido-bis(dimethylamido)diborane titanium allyl;
bis-2,6-dimethylbenzylamido-bis(dimethylamido)diborane titanium 11 4-1,4-diphenyl-1,3-butadiene;
bis-2,6-d imethylbenzylamido-bis (dim ethylamido)di bo rane titanium 114-2,4-hexadiene;
bis-2,6-dimethylbenzylamido-bis(dimethylamido)diborane titanium 11 4-1,4-dinaphthyl-1,3-butadiene;
bis-2,6-dimethylbenzyfamido-bis(dimethylamido)diborane titanium 'tl 4-1-phenyl-1,3-pentadiene;
SUBSTITUTE SHEET (RULE 26) bis-2,6-dimethylbenzyiamido-bis(dimethylamido)diborane titanium 114-1,3-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-diisopropyiphenylamido-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 11 4-1,4-diphenyl-1,3-butadiene;
bis-2,6-diisopropylphenylamido-bis(dimethylamido)diborane titanium r14-2,4-hexadiene;
bis-2,6-diisopropylphenylamido-bis(dimethylamido)diborane titanium 114-1,4-dinaphthyl-1,3-butadiene;
bis-2,6-diisopropylphenylamido-bis(dimethylamido)diborane titanium r1 4-1-phenyl-1,3-pentadiene;
bis-2,6-diisopropylphenylamido-bis(dimethylamido)diborane titanium q 4-1,3-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-diisopropyiphenylamido-bis(bis(trimethylsilyl)amido)diborane titanium bis-dimethyfamide;
bis-2,6-diisopropylphenylamido-bis(bis(trimethylsilyl)amido)diborane titanium 2-methyl-1,3-butadiene;
SUBSTITUTE SHEET (RULE 26) 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 ri 4-1,4-diphenyl-1,3-butadiene;
bis-2,6-diisopropylphenylamido-bis(bis(trimethylsilyl)amido)diborane titanium rj 4-2,4-hexadiene;
bis-2,6-diisopropyiphenylamido-bis(bis(trimethylsilyl)amido)diborane titanium rt4-1,4-dinaphthyl-1,3-butadiene;
bis-2,6-diisopropylphenylamido-bis(bis(trimethylsilyl)amido)diborane titanium 71 4-1 -phenyl-1,3-pentadiene;
bis-2,6-diisopropylphenylamido-bis(bis(trimethylsilyl)amido)diborane titanium r14-1,3-pentadiene;

bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diborane zirconium dichloride;
bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diborane zirconium dimethyl;
bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diborane zirconium bis-dimethylamide;
bis-2,6-diisopropylphenylarnido-bis(diisopropylamido)diborane zirconium 2-methyl-1,3-butadiene;
bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diborane zirconium 2,3-dimethyl-1,3-butadiene;
bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diborane zirconium 2-N, N-dimethylaminobenzyl;
bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diborane zirconium allyl;
bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diborane zirconium 71 4-1,4-diphenyl-1,3-butadiene;
bis-2,6-diisopropylphenylamido-bis(diisopropyfamido)diborane zirconium rl4-2,4-hexadiene;
SUBSTITUTE SHEET (RULE 26) bis-2,6-diisopropylphenylamido-bis(diisopropyiamido)diborane zirconium ri4-1,4-dinaphthyl-1,3-butadiene;
bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diborane zirconium ri4-1-phenyl-1,3-pentadiene;
bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diborane zirconium ri4-1,3-pentadiene;

bis-2-tert-butylphenylamido-bis(diisopropylamido)diborane titanium dichloride;
bis-2-tert-butylphenylamido-bis(diisopropylamido)diborane titanium dimethyl;
bis-2-tert-butylphenylamido-bis(diisopropyiamido)diborane titanium bis-dimethylamide;
bis-2-tert-butylphenylamido-bis(diisopropyfamido)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 allyi;
bis-2-tert-butylphenylamido-bis(diisopropylamido)diborane titanium 71 4-1,4-diphenyl-1,3-butadiene;
bis-2-tert butylphenylamido-bis(diisopropylamido)diborane titanium rj 4-2,4-hexadiene;
bis-2-tert-butylphenylamido-bis(diisopropylamido)diborane titanium 11 4-1,4-dinaphthyl-1,3-butadiene;
bis-2-tert-butylphenylamido-bis(diisopropylamido)diborane titanium 11 4-1-phenyi-1,3-pentadiene; and bis-2-tert-butylphenylamido-bis(diisopropylamido)diborane titanium q4-1,3-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 :

R1 R1 R' R1 IJ =O
R C Rl or R1 R1~ R Ri R
SUBSTITUTE SHEET (RULE 26) including such structures where two R' groups and R5 are linked such as in 1,3,4,6,7,8, hexahydro-pyrimido[1,2-a] pyrimidinate, shown below:

N
N

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-amidinate borane-bis-rl5-cyclopentadienylzirconium dichloride;
N,N"-diisopropyl-phenyl-amidinate borane-bis-rl5-cyclopentadienylzirconium dimethyl;
N, N "-diisopropyl-phenyl-amidinate borane-bis-rl5-cyclopentadienylzirconium bis-dimethylamide;
N,N "-diisopropyl-phenyl-amidinate borane-bis-rls-cyclopentadienylzirconium 2-methyl-1,3-butadiene;
N,N"-diisopropyl-phenyl-amidinate borane-bis-115-cyclopentadienylzirconium 2,3-dimethyl-1,3-butadiene;
N,N"-diisopropyl-phenyl-amidinate borane-bis-rl5-cyclopentadienylzirconium 2-N, N-dimethylaminobenzyl;
N,N"-diisopropyl-phenyl-amidinate borane-bis-rl5-cyclopentadienylzirconium allyl;
N,N'-diisopropyl-phenyl-amidinate borane-bis-rl5-cyclopentadienylzirconium r14-1,4-diphenyl-1,3-butadiene;
N,N "-diisopropyl-phenyl-amidinate borane-bis-rl5-cyclopentadienylzirconium ,14-2,4-hexadiene;
N,N "-dilsopropyl-phenyl-amidinate borane-bis-rl5-cyclopentadienylzirconium 11 4-1,4-dinaphthyl-1,3-butadiene;
N,N "-diisopropyl-phenyl-amidinate borane-bis-rl5-cyclopentadienylzirconium 714-1-phenyl-1,3-pentadiene;
N,N"-diisopropyl-phenyl-amidinate borane-bis-rl$-cyclopentadienylzirconium 7t4-1,3-pentadiene;
SUBSTITUTE SHEET (RULE 26) N, N'-diisopropyl-3-phenyl-1,3-diketimine borane-bis-rl5-cyclopentadienylzirconium dichloride;
N, N "-diisopropyl-3-phenyl-1,3-diketimine borane-bis-rl5-cyctopentadienylzirconium dimethyl;
N,N"-diisopropyl-3-phenyl-1,3-diketimine borane-bis-r15-cyclopentadienylzirconium bis-dimethylamide;
N,N "-diisopropyl-3-phenyl-1,3-diketimine borane-bis-rl5-cyclopentadienyizirconium 2-methyl-1,3-butadiene;
N,N "-diisopropyl-3-phenyl-1,3-diketimine borane-bis-TI5-cyclopentadienylzirconium 2,3-dimethyl-1,3-butadiene;
N, N "-diisopropyl-3-phenyl-l,3-diketimine borane-bis-rt5-cyclopentadienyizirconium 2-N,N-dimethylaminobenzyl;
N,N"-diisopropyl-3-phenyl-1,3-diketimine borane-bis-,qS-cyclopentadienylzirconium allyl;
N,N "-diisopropyl-3-phenyl-1,3-diketimine borane-bis-ll 5-cyclopentadienylzirconium r14-1,4-diphenyl-1,3-butadiene;
N,N "-diisopropyl-3-phenyl-1,3-diketimine borane-bis-rl5-cyclopentadienylzirconium r,4-2,4-hexadiene;
N,N "-diisopropyl-3-phenyl-1,3-diketimine borane-bis-rl5-cyclopentadienylzirconium rt4-1,4-dinaphthyl-1,3-butadiene;
N,N "-diisopropyl-3-phenyl-1,3-diketimine borane-bis-rl5-cyclopentadienylzirconium r14-1-phenyl-1,3-pentadiene;
N,N "-diisopropyl-3-phenyl-1,3-diketimine borane-bis-ri5-cyclopentadienylzirconium r14-1,3-pentadiene;
N,N "-diisopropyl-dimethylguanidinate borane-bis-rl5-cyclopentadienylzirconium dichforide;
N,N "-diisopropyl-dimethylguanidinate borane-bis-rl5-cyclopentadienylzirconium dimethyl;
N,N"-diisopropyl-dimethylguanidinate borane-bis-rt5-cyciopentadienyizirconium bis-dimethylamide;
N,N "-diisopropyl-dimethylguanidinate borane-bis-rt5-cyclopentadienylzirconium 2-methyl-1,3-butadiene;
SUBSTITUTE SHEET (RULE 26) N, N'-diisopropyl-dimethylguanidinate borane-bis-ri5-cyclopentadienylzirconium 2,3-dimethyl-1,3-butadiene;
N,N'-diisopropyl-dimethylguanidinate borane-bis-rt5-cyclopentadienylzirconium 2-N,N-dimethylaminobenzyl;
N,N'-diisopropyl-dimethylguanidinate borane-bis-ri5-cycfopentadienyizirconium allyl;
N, N'-diisopropyl-dimethylguanidinate borane-bis-rl5-cyclopentadienylzirconium r14-1,4-diphenyl-1,3-butadiene;
N,N'-diisopropyl-dimethylguanidinate borane-bis-.q5-cyclopentadienylzirconium r14-2,4-hexadiene;
N, N'-diisopropyl-dimethylguanidinate borane-bis-ri5-cyclopentadienylzirconium 114-1,4-dinaphthyl-1,3-butadiene;
N,N'-diisopropyl-dimethylguanidinate borane-bis-ri'-cyclopentadienyizirconium r14-1-phenyl-1,3-pentadiene;
N,N'-diisopropyl-dimethylguanidinate borane-bis-ris-cyclopentadienylzirconium ri4-1,3-pentadiene;
1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinate borane-bis-ri5-inden-l-ylzirconium dichloride;
1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinate borane-bis-ri5-inden-1-ylzirconium dimethyl;
1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinate borane-bis-ll 5-inden-l-ylzirconium bis-dimethylamide;
1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinate borane-bis-ri5-inden-l-ylzirconium 2-methyl-1,3-butadiene;
1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinate borane-bis-rt5-inden-1 -ylzirconium 2,3-dimethyl-1,3-butadiene;
1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinate borane-bis-,n5-inden-1-ylzirconium 2-N,N-dimethylaminobenzyl;
1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinate borane-bis-ri5-inden-1 -ylzirconium allyl;
1,3,4,6,7,8-hexahydro-pyrirnido[1,2-a] pyrimidinate borane-bis-715-inden-1 -ylzirconium ri4-1,4-diphenyl-1,3-butadiene;
SUBSTITUTE SHEET (RULE 26) 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinate borane-bis-ri5-inden-l-ylzirconium ri4-2,4-hexadiene;
1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinate borane-bis-,q5-inden-i-ylzirconium ri4-1,4-dinaphthyl-1,3-butadiene;
1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinate borane-bis-ri5-inden-1-ylzirconium ri4-l-phenyl-1,3-pentadiene;
1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinate borane-bis-rt$-inden-l-ylzirconium r14-1,3-pentadiene;

N,N'-diisopropyl-phenyl-amidinate borane-bis-ri5-(2-methylinden-1-yl)zirconium dichioride;
N, N'-diisopropyl-phenyl-amidinate borane-bis-ri5-(2-methylinden-1-yl)zirconium dimethyl;
N,N'-diisopropyl-phenyl-amidinate borane-bis-ri5-(2-methylinden-l-yI)zirconium bis-dimethylamide;
N,N'-diisopropyl-phenyl-amidinate borane-bis-rl5-(2-methylinden-l-yl)zirconium 2-methyE-1,3-butadiene;
N, N'-diisopropyl-phenyl-amidinate borane-bis-,q5-(2-methylinden-l-yl)zirconium 2,3-dimethyl-1,3-butadiene;
N,N'-diisopropyl-phenyl-amidinate borane-bis-,95-(2-methylinden-1-yI)zirconium 2-N,N-dimethylaminobenzyl;
N,N'-diisopropyl-phenyf-amidinate borane-bis-rt5-(2-methylinden-l-yI)zirconium allyi;
N,N'-diisopropyi-phenyl-amidinate borane-bis-rl5-(2-methylinden-1-yl)zirconium r14-1,4-diphenyl-1,3-butadiene;
N, N'-diisopropyl-phenyl-amidinate borane-bis-rt5-(2-methylinden-1-yI)zirconium r14-2,4-hexadiene;
N,N'-diisopropyl-phenyl-amidinate borane-bis-rl5-(2-methylinden-1-yI)zirconium r14-1,4-dinaphthyl-1,3-butadiene;
N,N'-diisopropyl-phenyl-amidinate borane-bis-rl5-(2-methylinden-1-yl)zirconium ri4-l-phenyl-1,3-pentadiene;
N,N'-diisopropyl-phenyl-amidinate borane-bis-rl5-(2-methylinden-l-yI)zirconium r14-1,3-pentadiene;
SUBSTITUTE SHEET (RULE 26) N,N'-bis-2,6-diisopropylphenyl-phenyl-amidinate borane-bis-rls-(2-methyl-4-phenylinden-1-yi)zirconium dichloride;
N, N'-bis-2,6-diisopropylphenyi-phenyi-amidinate borane-bis-,q5-(2-methyl-4-phenylinden-1-yi)zirconium dimethyl;
N,N'-bis-2,6-diisopropylphenyl-phenyl-amidinate borane-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium bis-dimethylamide;
N,N'-bis-2,6-diisopropylphenyl-phenyl-amidinate borane-bis-,q 5-(2-methyl-4-phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
N,N'-bis-2,6-diisopropylphenyl-phenyl-amidinate borane-bis-rl5-(2-methyl-4-phenylinden-l-yl)zirconium 2,3-dimethyl-l,3-butadiene;
N,N'-bis-2,6-diisopropylphenyl-phenyl-amidinate borane-bis-,q5-(2-methyl-4-phenylinden-1-yl)zirconium 2-N, N-dimethylaminobenzyl;
N,N'-bis-2,6-diisopropylphenyl-phenyl-amidinate borane-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium allyl;
N,N'-bis-2,6-diisopropylphenyl-phenyl-amidinate borane-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium r14-1,4-diphenyl-1,3-butadiene;
N,N'-bis-2,6-diisopropylphenyl-phenyl-amidinate borane-bis-rl 5-(2-methyl-4-phenylinden-1 -yl)zirconium r14-2,4-hexadiene;
N,N'-bis-2,6-diisopropyiphenyi-phenyl-amidinate borane-bis-rls-(2-methyl-4-phenylinden-1-yl)zirconium rt4-1,4-dinaphthyl-1,3-butadiene;
N,N'-bis-2,6-diisopropylphenyl-phenyl-amidinate borane-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium 114-1-phenyl-1,3-pentadiene;
N, N "-bis-2,6-diisopropylphenyl-phenyl-amidinate borane-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium r14-1,3-pentadiene;
N,N'-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium dichloride;
N,N'-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis-rl5-(2-methyl-4-phenylinden-1-yi)zirconium dimethyl;
N,N'-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium bis-dimethylamide;
N,N'-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis-r,5-(2-methyl-4-phenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
. -68-SUBSTITUTE SHEET (RULE 26) N,N'-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis-r15-(2-methyl-4-phenylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
N,N'-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis-rl5-(2-methyl-4-phenylinden-l-yl)zirconium 2-N,N-dimethylaminobenzyl;
N,N'-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis-ri5-(2-methyl-4-phenylinden-1-yl)zirconium allyl;
N,N'-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis-,n5-(2-methyl-4-phenylinden-1-yl)zirconium ri4-1,4-diphenyl-l,3-butadiene;
N,N'-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis-rls-(2-methyl-4-phenylinden-1-yl)zirconium r14-2,4-hexadiene;
N,N'-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium r,4-1,4-dinaphthyl-1,3-butadiene;
N,N'-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis-il5-(2-methyl-4-phenylinden-1-yl)zirconium r14-l-phenyl-1,3-pentadiene;
N,N'-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimine borane-bis-,n5-(2-methyt-4-phenylinden-1-yl)zirconium r,4-1,3-pentadiene;

bis(N, N'-diisopropyl-phenyl-amidinate)diborane-1,2-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium dichloride;
bis(N,N'-diisopropyl-phenyl-amidinate)diborane-1,2-bis-lI 5-(2-methyl-4-phenyiinden-1-yl)zirconium dimethyl;
bis(N, N'-diisopropyl-phenyl-amidinate)diborane-1,2-bis-rI 5 -(2-methyl-4-phenylinden-1 -yl)zirconium bis-dimethylamide;
bis(N, N'-diisopropyi-phenyl-amidinate)diborane-1,2-bis-rls-(2-methyl-4-phenylinden-1 -yl)zirconium 2-methyl-1,3-butadiene;
bis(N, N'-diisopropyl-phenyl-amidinate)diborane-l,2-bis-,q5-(2-methyl-4-phenylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
bis(N,N'-diisopropyl-phenyl-amidinate)diborane-1,2-bis-rl5-(2-methyl-4-phenylinden-l-yl)zirconium 2-N,N-dimethylaminobenzyl;
bis(N,N'-diisopropyl-phenyl-amidinate)diborane-1,2-bis-ri5-(2-methyl-4-phenylinden-1-yl)zirconium allyl;
bis(N, N'-diisopropyl-phenyl-amidinate)diborane-1,2-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium ri4-1,4-diphenyl-1,3-butadiene;

SUBSTITUTE SHEET (RULE 26) bis(N,N'-diisopropyl-phenyl-amidinate)diborane-1,2-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium q4-2,4-hexadiene;
bis(N, N'-diisopropyl-phenyl-amidinate)diborane-1,2-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium ri4-1,4-dinaphthyl-1,3-butadiene;
bis(N,N'-diisopropyl-phenyl-amidinate)diborane-1,2-bis-rl5-(2-methyl-4-phenylinden-l-yl)zirconium ,14-1-phenyl-l,3-pentadiene;
bis(N, N'-diisopropyl-phenyl-amidinate)diborane-1,2-bis-rl5-(2-methyl-4-phenylinden-l-yl)zirconium 11 -1,3-pentadiene;

bis(N,N'-diisopropyl-3-phenyl-1,3-diketimine)diborane-1,2-bis-rl5-(2-methyl-4-phenyiinden-1-yl)zirconium dichloride;
bis(N,N'-diisopropyl-3-phenyl-1,3-diketimine)diborane-1,2-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium dimethyl;
bis(N,N'-diisopropyl-3-phenyl-1,3-diketimine)diborane-1,2-bis-rl5-(2-methyl-4-phenyfinden-1-yl)zirconium bis-dimethylamide;
bis(N,N "-diisopropyl-3-phenyl-1,3-diketimine)diborane-l,2-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium 2-methyl-1 ,3-butadiene;
bis(N, N'-diisopropyi-3-phenyl-1,3-diketimine)diborane-1,2-bis-r15-(2-methyl-4-phenylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;
bis(N,N'-diisopropyl-3-phenyl-l,3-diketimine)diborane-l,2-bis-rl5-(2-methyl-4-phenylinden-l-yl)zirconium 2-N,N-dimethylaminobenzyl;
bis(N, N'-diisopropyl-3-phenyl-1,3-diketimine)diborane-1,2-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium allyl;
bis( N, N'-diisopropyl-3-phenyl-1,3-diketi mine)diborane-1, 2-bis-rl5-(2-methyl-4-phenylinden-l-yl)zirconium r14-1,4-diphenyl-1,3-butadiene;
bis(N, N'-diisopropyi-3-phenyl-1,3-diketimine)diborane-1,2-bis-.q 5-(2-methyl-phenylinden-l-yl)zirconium ri4-2,4-hexadiene;
bis(N, N'-diisopropyl-3-phenyl-1,3-diketimine)diborane-1,2-bis-rl5-(2-methyl-4-phenylinden-l-yl)zirconium n4-1,4-dinaphthyl-1,3-butadiene;
bis(N,N"-diisopropyl-3-phenyl-1,3-diketimine)diborane-1,2-bis-,n5-(2-methyl-4-phenylinden-1-yl)zirconium r14-1-phenyl-1,3-pentadiene;
bis(N, N'-diisopropyl-3-phenyl-1,3-diketimine)diborane-1,2-bis-r15-(2-methyl-4-phenylinden-1-yl)zirconium 11 -1,3-pentadiene;

SUBSTITUTE SHEET (RULE 26) N,N'-diisopropyl-phenyl-amidinate borane-bis-rl5-(2-methyl-4-naphthylinden-1-yI)zirconium dichloride;
N,N'-diisopropyl-phenyl-amidinate borane-bis-rt5-(2-methyl-4- naphthyfinden-1-yl)zirconium dimethyl;
N,N'-diisopropyl-phenyl-amidinate borane-bis-r15-(2-methyl-4- naphthylinden-1 -yl)zirconium bis-dimethylamide;
N, N'-diisopropyl-phenyl-amidinate borane-bis-rl5-(2-methyl-4- naphthylinden-1-yl)zirconium 2-methyl-1,3-butadiene;
N,N'-diisopropyl-phenyl-amidinate borane-bis-ri5-(2-methyi-4- naphthylinden-1 -yl)zirconium 2,3-dimethyl-1,3-butadiene; .
N,N'-diisopropyl-phenyl-amidinate borane-bis-rl5-(2-methyl-4- naphthylinden-1 -yl)zirconium 2-N,N-dimethylaminobenzyl;
N, N'-diisopropyl-phenyl-amidinate borane-bis-ris-(2-methyl-4- naphthy(inden-1-yf)zirconium allyl;
N,N'-diisopropyi-phenyl-amidinate borane-bis-rl5-(2-methyl-4- naphthylinden-1 -yl)zirconium 114-1,4-diphenyl-1,3-butadiene;
N, N'-diisopropyl-phenyl-amidinate borane-bis-ri5-(2-methyl-4- naphthylinden-1-yl)zirconium 11 -2,4-hexadiene;
N, N'-diisopropyl-phenyl-amidinate borane-bis-,n5-(2-methyl-4- naphthylinden-1-yl)zirconium 11 -1,4-dinaphthyl-1,3-butadiene;
N, N'-diisopropyl-phenyl-amidinate borane-bis-,q5-(2-methyl-4- naphthylinden-1-yl)zirconium 11 -1-phenyl-1,3-pentadiene;
N,N'-diisopropyl-phenyl-amidinate borane-bis-rl5-(2-methyl-4- naphthylinden-1 -yl)zirconium ri4-1,3-pentadiene;
N,N'-diisopropyl-3-phenyl-1,3-diketimine borane-bis-,95-(2-methyl-4-naphthylinden-1-yl)zirconium dichloride;
N,N'-diisopropyl-3-phenyl-l,3-diketimine borane-bis-,qs-(2-methyl-4-naphthylinden-l-yl)zirconium dimethyl;
N,N'-diisopropyl-3-phenyl-1,3-diketimine borane-bis-rl5-(2-methyl-4-naphthylinden-l-yl)zirconium bis-dimethylamide;
N,N'-diisopropyl-3-phenyl-1,3-diketimine borane-bis-ri5-(2-methyl-4-naphthylinden-l-yl)zirconium 2-methyl-1,3-butadiene;

SUBSTITUTE SHEET (RULE 26) N, N'-diisopropyl-3-phenyl-l,3-diketimine borane-bis-,q5-(2-methyl-4-naphthylinden-l-yl)zirconium 2,3-dimethyl- 1,3-butadiene;
N,N'-diisopropyl-3-phenyl-1,3-diketimine borane-bis-rt5-(2-methyl-4-naphthylinden-l-yl)zirconium 2-N,N-dimethylaminobenzyl;
N,N'-diisopropyl-3-phenyl-1,3-diketimine borane-bis-71 5-(2-methyl-4-naphthylinden-1-yl)zirconium allyl;
N,N'-diisopropyl-3-phenyl-1,3-diketimine borane-bis-,q 5-(2-methyl-4-naphthylinden-1-yi)zirconium r14-1,4-diphenyl-1,3-butadiene;
N,N'-diisopropyl-3-phenyl-1,3-diketimine borane-bis-rt5-(2-methyl-4-naphthylinden-1-yi)zirconium rt4-2,4-hexadiene;
N, N'-diisopropyl-3-phenyl-1,3-diketimine borane-bis-rt5-(2-methyl-4-naphthylinden-1-yl)zirconium q 4-1,4-dinaphthyl-1,3-butadiene;
N,N "-diisopropyl-3-phenyl-1,3-diketimine borane-bis-rl 5-(2-methyl-4-naphthylinden-1-yl)zirconium r14-1-phenyl-1,3-pentadiene;
N,N'-diisopropyl-3-phenyl-1,3-diketimine borane-bis-115-(2-methyl-4-naphthylinden-1-yl)zirconium ,14-1,3-pentadiene;
bis-2,6-diisopropylphenylamido-bis(N,N'-diisopropyl-phenyl-amidinate)diborane titanium dichloride;
bis-2,6-diisopropylphenylamido-bis(N,N'-diisopropyl-phenyl-amidinate)diborane titanium dimethyl;
bis-2, 6-diisopropylphenylamido-bis(N, N'-diisopropyl-phenyl-amidinate)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)diborane titanium allyl;
bis-2,6-diisopropylphenylamido-bis(N,N"-diisopropyl-phenyl-amidinate)diborane titanium r14-1,4-diphenyl-1,3-butadiene;
bis-2,6-diisopropylphenylamido-bis(N,N'-diisopropyl-phenyl-amidinate)diborane titanium r14-2,4-hexadiene;

SUBSTITUTE SHEET (RULE 26) bis-2,6-diisopropylphenylamido-bis(N,N "-diisopropyl-phenyl-amidinate)diborane titanium 11 -1,4-dinaphthyl-1,3-butadiene;
bis-2,6-diisopropylphenylamido-bis(N, N "-diisopropyl-phenyl-amidinate)diborane titanium 11 -1-phenyl-1,3-pentadiene;
bis-2,6-diisopropytphenyfamido-bis(N,N"-diisopropyl-phenyl-amidinate)diborane titanium r14-1,3-pentadiene;
bis-2,6-diisopropylphenylamido-bis(N,N "-diisopropyl-3-phenyl-1,3-diketimine)diborane titanium dichloride;
bis-2,6-diisopropyfphenylamido-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-l,3-diketimine)diborane titanium allyl;
bis-2,6-diisopropylphenylamido-bis(N,N "-diisopropyl-3-phenyl-l,3-diketimine)diborane titanium ri4-1,4-diphenyl-l,3-butadiene;
bis-2,6-diisopropylphenylamido-bis(N,N"-diisopropyl-3-phenyl-1,3-diketimine)diborane titanium ri4-2,4-hexadiene;
bis-2,6-diisopropyiphenylamido-bis(N, N'-diisopropyl-3-phenyl-1,3-diketimine)diborane titanium ri4-1,4-dinaphthyl-1,3-butadiene;
bis-2,6-diisopropylphenylamido-bis(N,N "-diisopropyl-3-phenyl-1,3-diketimine)diborane titanium ri4-l-phenyl-1,3-pentadiene; and bis-2,6-diisopropylphenylamido-bis(N,N "-diisopropyl-3-phenyl-1,3-diketimine)diborane titanium ri4-1,3-pentadiene.
The skilled artisan 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 the terms ri5 or,14 may not accurately reflect the actual electronic distribution of the molecule under use SUBSTITUTE SHEET (RULE 26) conditions, and that molecules including lesser numbers of contributing atoms to the electronic delocation are intended to be included within such descriptions as well.
The most highly preferred metal complexes are dimethylamidoborane-bis(rt5-cyclopentadienyl)zirconium dichloride, dimethylamidoboranebis(r15-inden-1-yl)zirconium dichloride, dimethylamidoborane-bis(rl5-2-methyl-4-phenylinden-1-yl)zirconium dichloride, dimethylamidoborane-bis(rt5-2-ethyl-4-phenylinden-1-yl)zirconium dichloride, dimethylamidoborane-bis(r15-2-isopropyl-4-phenylinden-l-yl)zirconium dichloride, dimethylamidoborane-bis(r15-2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium dichioride, dimethylamidoborane-bis(r15-3-t-butylinden-1 -yl)zirconium dichloride, diisopropylamidoborane-bis(,n5-cyclopentadienyl)zirconium dichloride, diisopropylamidoboranebis(rl5-inden-l-yl)zirconium dichloride, diisopropylamidoborane-bis(,n5-2-methyl-4-phenylinden-1-yl)zirconium dichloride, diisopropylamidoborane-bis(r15-2-ethyl-4-phenylinden-1-yl)zirconium dichloride, diisopropylamidoborane-bis(r15-2-isopropyl-4-phenylinden-l-yl)zirconium dichloride, diisopropylamidoborane-bis(.q5-2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-yl)zirconium dichloride, diisopropylamidoborane-bis(r]5-3-t-butylinden-1-yl)zirconium dichloride, diphenyfamidoborane-bis(rl5-cyclopentadienyl)zirconium dichloride, diphenyiamidoboranebis(115-inden-1-yl)zirconium dichloride, diphenylamidoborane-bis(r15-2-methyl-4-phenylinden-1-yl)zirconium dichloride, diphenylamidoborane-bis(il 5-2-ethyl-4-phenylinden-1-yl)zirconium dichloride, diphenylamidoborane-bis(rJ5-2-isopropyl-4-phenylinden-1-yl)zirconium dichloride, diphenylamidoborane-bis(rj methyl-4-bis(3,5-trifluoromethyl)phenylinden-l-yl)zirconium dichloride, diphenylamidoborane-bis(rl5-3-t-butylinden-1-yl)zirconium dichloride, dimethylamidoborane-bis(rl5-cyclopentadienyl)zirconium 1,4-diphenyl-1,3-butadiene, dimethylamidoboranebis(r15-inden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, dimethylamidoborane-bis(il5-2-methyl-4-phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, dimethylamidoborane-bis(115-2-ethyl-4-phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, dimethylamidoborane-bis(r15-2-isopropyl-4-phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, dimethylamidoborane-bis(rt5-2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-l-yl)zirconium 1,4-diphenyl-1,3-butadiene, dimethylamidoborane-bis(r15-3-t-butylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, SUBSTITUTE SHEET (RULE 26) diisopropylamidoborane-bis(ri5-cyclopentadienyl)zirconium 1,4-diphenyl-1,3-butadiene, diisopropylamidoboranebis(ri5-inden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, diisopropylamidoborane-bis(ri5-2-methyl-4-phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, diisopropylamidoborane-bis(ri5-2-ethyl-4-phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, diisopropylamidoborane-bis(ri5-2-isopropyl-4-phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, diisopropylamidoborane-bis(rt5-2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, diisopropylamidoborane-bis(ri5-3-t-butylinden-1-yi)zirconium 1,4-diphenyl-1,3-butadiene, diphenylamidoborane-bis(,q5-cyclopentadienyl)zirconium 1,4-diphenyl-1,3-butadiene, diphenylamidoboranebis(rl5-inden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, diphenylamidoborane-bis(ris-2-methyl-4-phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, diphenylamidoborane-bis(ri5-2-ethyl-4-phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, diphenylamidoborane-bis(ri5-2-isopropyl-4-phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, diphenylamidoborane-bis(ri5-2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-l-yl)zirconium 1,4-diphenyl-1,3-butadiene, and diphenylamidoborane-bis(ri5-3-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 1 a and 2a to a dianionic salt (where R4 is H) via reaction with a metal amide such as sodium bis(trimethylsilyl)amide or lithium bis(trimethylsilyl)amide. The dianionic ligand derivative is then reacted with a metal complex precursor such as MY34r MY33i or MY32 (and the corresponding Lewis base adducts), where Y3 is defined as above. Altematively, reactions employing the neutral ligand, where R4 is hydrogen, in combination with the metal precursors M(NR32)4 or MR3a can be employed. (Preparation of the ligands of formula 2a where Y" and Y2'are each an NR' group can be readily accomplished by contacting a diboron tetrahydrocarbyloxide compound of the formula ((R'O)zB)2r where R' is 10 hydrocarbyl, or two R' groups together are C2_2o dihydrocarbyl, especially bis(catecholato)diboron with an alkali metal C1.4 dihydrocarbylamide, especially lithium dimethylamide.) All of the foregoing reactions are conducted in an inert solvent such as a hydrocarbon solvent or an etheral solvent in the temperature range of -100 2C to 150 C.
An especially useful metal complex precursor reagent corresponds to the formula 3:

SUBSTITUTE SI1EET (RULE 26) . 44285 Rs ~ I ~ R6 LBLB
Y~ Y3 Formula 3 , wherein M is zirconium, Rs 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.
Altematively, where R4 in structures of formula 1 a 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. Altematively, 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 oiefin 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)aluminum- 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 combinations of the foregoing activating cocatalysts and techniques. The foregoing activating cocatalysts and activating techniques have AMENDED SHEET

. 64693-5519 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 US-A-6,395,671.
Combinations of neutral Lewis acids, especially the combination of a trialkylaluminum compound having from 1 to 4 carbons in each alkyl group and a halogenated tri(hydrocarbyi)boron compound having from 1 to 20 carbons in each hydrocarbyl group, especially tris(pentafluorophenyi)borane, further combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane, and combinations 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-phenylborane:aiumoxane 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 Bronsted acid capable of donating a proton, and a compatible, noncoc.krdinating anion, A-. As used herein, the term "noncoordinating" means 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 transfer an anionic substituent or fragment thereof to said cation thereby forming neutral complexes. "Compatible anions" are anions which are not degraded to neutrality when the initially formed complex decomposes and are noninterfering with desired subsequent polymerization or other uses of the complex.
Preferred anions 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 unsaturated compounds or other neutral Lewis bases such as ethers or nitriles. Suitable metals include, but are not limited to, aluminum, gold and platinum. Suitable metalloids include, but are not limited to, boron, phosphorus, and silicon. Compounds containing anions 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)d+ (A)d-wherein:
L* is a neutral Lewis base;

(L*-H)+ is a conjugate Bronsted 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 A`" 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 carbons 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-, fluorohydrocarbyl-, fluorohydrocarbyloxy-hydroxyfluorohydrocarbyl-, dihydrocarbylaluminumoxyfluorohydrocarbyl-, or fluorinated silylhydrocarbyl- group of up to 20 nonhydrogen atoms, with the proviso that in not more than one occasion is Q hydrocarbyl.

SUBSTITUTE SHEET (RULE 26) 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-dimethylanilinium tetrakis(pentafluorophenyl) borate, N,N-dimethylanifinium n-butyltris(pentafluorophenyl) borate, N,N-dimethylanilinium benzyltris(pentafluorophenyl) borate, N,N-dimethylanilinium tetrakis(4-(t-butyidimethylsilyl)-2, 3, 5, 6-tetrafluorophenyl) borate, N,N-dimethyianilinium tetrakis(4-(triisopropylsifyl)-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, dimethyloctadecyfammonium tetrakis(pentafluorophenyl) borate, methylditetradecylammonium tetrakis(pentafluorophenyl) borate, methyiditetradecylammonium (hydroxyphenyl)tris(pentafluorophenyl) borate, methyiditetradecylammonium (diethylaluminoxyphenyl)tris(pentafluorophenyl) borate, methyidihexadecylammonium tetrakis(pentafluorophenyl) borate, methyldihexadecylammonium (hydroxyphenyl)tris(pentafluorophenyl) borate, methyldihexadecylammonium (diethylaluminoxyphenyl)tris(pentafluorophenyl) borate, methyldioctadecylammonium tetrakis(pentafluorophenyl) borate, methyidioctadecylammonium (hydroxyphenyl)tris(pentafluorophenyl) borate, methyidioctadecylamrnonium (diethylaluminoxyphenyl)tris(pentafluorophenyl) borate, mixtures of the foregoing, dialkyl ammonium salts such as:

SUBSTITUTE SHEET (RULE 26) 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 methyidioctadecylammonium and dimethyloctadecylammonium.
Another suitable ion forming, activating cocatalyst comprises a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the formula:
(Oxe+)d(Ad )e.
wherein:
Oxe* 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 Pb+2. Preferred embodiments of Ad' 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 C,_20 carbenium ion; and SUBSTITUTE SHEET (RULE 26) 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:
R3Si(X')q`A"
wherein:
R is C,_,o 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 W096/08519 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: (A'+a')b1(Z'J'j1)-c1 dl, wherein:
A' is a cation of charge +a', Z' 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;
J' independently each occurrence is a Lewis acid coordinated to at least one Lewis base site of Z', and optionally two or more such J' groups may be joined together in a moiety having multiple Lewis acidic functionality, j' is a number from 2 to 12 and a', b', c, and d' are integers from 1 to 3, with the proviso that a' x b' is equal to c' x d'.
The foregoing cocatalysts (illustrated by those having imidazolide, substituted imidazolide, imidazolinide, substituted imidazolinide, benzimidazolide, or substituted benzimidazolide anions) may be depicted schematically as follows:

SUBSTITUTE SHEET (RULE 26) 1+ N ~
A N_J1 A1J1_ N-~_:- N_J1 Ai+ J1 $_N J1 ~--O~ )--- or R8 R8 (R~2 (R8)2 R8 R8 wherein:
A'+ is a monovalent cation as previously defined, and preferably is a trihydrocarbyl ammonium cation, containing one or two C1o-4o 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 C,_20 alkyl, and J' is tris(pentafluorophenyl)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)borane)imidazolide, bis(tris(pentafluorophenyl)borane)-2-undecylimidazolide, bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolide, bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolide, bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolide, bis(tris(pentafluorophenyl)borane)imidazolinide, bis(tris(pentafluorophenyl)borane)-2-undecylimidazoiinide, bis(tris(pentafiuorophenyl)borane)-2-heptadecylimidazolinide, bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolinide, bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyi)imidazolinide, bis(tris(pentafluorophenyl)borane)-5,6-dimethylbenzimidazolide, bis(tris(pentafluorophenyl)borane)-5,6-bis(undecyl)benzimidazolide, bis(tris(pentafluorophenyl)alumane)imidazolide, bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolide, bis(tris(pentafluorophenyl)aiumane)-2-heptadecylimidazolide, bis(tris(pentafluorophenyi)alumane)-4,5-bis(undecyl)imidazolide, bis(tris(pentafluorophenyi)alumane)-4,5-bis(heptadecyl)imidazolide, SUBSTITUTE SHEET (RULE 26) WO 00/20426 PCT/US99l20538 bis(tris(pentafluorophenyl)alumane)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 technique of bulk electrolysis involves the electrochemical oxidation of the metal complex under electrolysis conditions in the presence of a supporting electrolyte comprising a noncoordinating, inert anion. In the technique, solvents, supporting electrolytes and electrolytic potentials for the electrolysis are used such that electrolysis byproducts that would render the metal complex catalytically inactive are not substantially formed during the reaction. More particularly, suitable solvents are materials that are: liquids under the conditions of the electrolysis (generally temperatures from 0 to 100 C), capable of dissolving the supporting electrolyte, and inert. "Inert solvents" are those that are not reduced or oxidized under the reaction conditions employed for the electrolysis. It is generally possible in view of the desired electrolysis reaction to choose a solvent and a supporting electrolyte that are unaffected by the electrical potential used for the desired electrolysis.
Preferred solvents include difluorobenzene (all isomers), dimethoxyethane (DME), and mixtures thereof.
The electrolysis may be conducted in a standard electrolytic cell containing an anode and cathode (also referred to as the working electrode and counter electrode respectively). Suitable materials of construction for the cell are glass, plastic, ceramic and glass coated metal. The electrodes are prepared from inert conductive materials, by which are meant conductive materials that are unaffected by the reaction mixture or reaction conditions. Platinum or palladium are preferred inert conductive materials.
Normally an ion permeable membrane such as a fine glass frit separates the cell into separate compartments, the working electrode compartment and counter electrode compartment. The working electrode is immersed in a reaction medium comprising the metal complex to be activated, solvent, supporting electrolyte, and any other materials desired for moderating the electrolysis or stabilizing the resulting complex.
The counter electrode is immersed in a mixture of the solvent and supporting electrolyte. The desired voltage may be determined by theoretical calculations or experimentally by sweeping the cell using a reference electrode such as a silver electrode immersed in the cell electrolyte. The background cell current, the current SUBSTITUTE SHEET (RULE 26) draw in the absence of the desired electrolysis, is also determined. The electrolysis is completed when the current drops from the desired level to the background level.
In this manner, complete conversion of the initial metal complex can be easily detected.
Suitable supporting electrolytes are salts comprising a cation and a compatible, noncoordinating anion, A-. Preferred supporting electrolytes are salts corresponding to the formula G+A"; wherein:
G+ is a cation which is nonreactive towards the starting and resulting complex, and A' is as previously defined.
Examples of cations, G+, include tetrahydrocarbyl substituted ammonium or phosphonium cations having up to 40 nonhydrogen atoms. Preferred cations are the tetra(n-butylammonium)- and tetraethylammonium- cations.
During activation of the complexes of the present invention by bulk electrolysis the cation of the supporting electrolyte passes to the counter electrode and A-migrates to the working electrode to become the anion of the resulting oxidized product. Either the solvent or the cation of the supporting electrolyte is reduced at the counter electrode in equal molar quantity with the amount of oxidized metal complex formed at the working electrode. Preferred supporting electrolytes are tetrahydrocarbylammonium salts of tetrakis(perfluoroaryl) borates having from 1 to 10 carbons in each hydrocarbyl or perfluoroaryl group, especially tetra(n-butylammonium)tetrakis(pentafluorophenyl) borate.
A further recently discovered electrochemical technique for generation of activating cocatalysts is the electrolysis of a disilane compound in the presence of a source of a noncoordinating compatible anion. This technique is more fully disclosed and claimed in the previously mentioned United States Patent application serial number 304,314, published in eqauivalent form as W096/08519.
The foregoing electrochemical activating technique and activating cocatalysts may also be used in combination. An especially preferred combination is a mixture of a tri(hydrocarbyl)aluminum or tri(hydrocarbyl)borane compound having from 1 to carbons in each hydrocarbyl group with an oligomeric or polymeric alumoxane compound.
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 SUBSTITUTE SHEET (RULE 26) 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 approximately equimolar quantity with the metal complex.
The catalysts, whether or not supported in any of the foregoing methods, may be used to polymerize ethylenically and/or acetylenically unsaturated monomers having from 2 to 100,000 carbon atoms either alone or in combination.
Preferred monomers include the C2-20 a-olefins especially ethylene, propylene, isobutylene, 1-butene, 1 -pentene, 1 -hexene, 3-methyl-1 -pentene, 4-methyl-1 -pentene, 1-octene, 1-decene, long chain macromolecular a-olefins, and mixtures thereof. Other preferred monomers include styrene, C1-4 alkyl substituted styrene, tetrafluoroethylene, vinylbenzocyclobutane, ethylidenenorbomene, 1,4-hexadiene, 1,7-octadiene, vinylcyclohexane, 4-vinylcyclohexene, divinylbenzene, and mixtures thereof with ethylene. Long chain macromolecular a-olefins are vinyl terminated polymeric remnants formed in situ during continuous solution polymerization reactions.
Under suitable processing conditions such long chain macromolecular units are readily polymerized into the polymer product along with ethylene and other short chain olef in monomers to give small quantities of long chain branching in the resulting polymer.
Preferred monomers include a combination of ethylene and one or more comonomers selected from monovinyl aromatic monomers, 4-vinylcyclohexene, vinylcyclohexane, norbornadiene, ethylidene-norbomene, C3-10 aliphatic a-olefins (especially propylene, isobutylene, 1 -butene, 1 -hexene, 3-methyl-l-pentene, methyl-1 -pentene, and 1 -octene), and C4-40 dienes. Most preferred monomers are mixtures of ethylene and styrene; mixtures of ethylene, propylene and styrene;
mixtures of ethylene, styrene and a nonconjugated diene, especially ethylidenenorbornene or 1,4-hexadiene, and mixtures of ethylene, propylene and a nonconjugated diene, especially ethylidenenorbornene or 1,4-hexadiene.
In general, the polymerization may be accomplished at conditions well known in the prior art for Ziegler-Natta or Kaminsky-Sinn type polymerization reactions, that is, temperatures from 0-250 C, preferably 30 to 200 C and pressures from atmospheric to 10,000 atmospheres. Suspension, solution, slurry, gas phase, solid state powder polymerization or other process condition may be employed if desired.
A support, especially silica, alumina, or a polymer (especially poly(tetrafluoroethylene) or a polyolefin) may be employed, and desirably is employed when the catalysts are used in a gas phase polymerization process. The support is SUBSTITUTE SHEET (RULE 26) 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 reactions the molar ratio of catalyst:polymerizable compounds employed is from 10"12:1 to 10"1:1, more preferably from 10'9:1 to 10'5:1.
Suitable solvents use for solution polymerization are inert liquids. Examples include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; perfluorinated hydrocarbons such as perfluorinated C4-10 alkanes, and alkyl-substituted aromatic compounds such as benzene, toluene, xylene, and ethylbenzene. Suitable solvents also include liquid olef ins which may act as monomers or comonomers.
The catalysts may be utilized in combination with at least one additional homogeneous or heterogeneous polymerization catalyst in the same reactor or in separate reactors connected in series or in parallel to prepare polymer blends having desirable properties. An example of such a process is disclosed in WO
94/00500, equivalent to U. S. Serial Number 07/904,770, as well as U. S. Serial Number 08/10958, filed January 29, 1993.
Utilizing the present catalysts, a-olefin homopolymers and copolymers having densities from 0.85 g/cm3 to 0.96 g/cm3, and melt flow rates from 0.001 to 1000.0 dg/min are readily attained in a highly efficient process.
The catalysts of the present invention are particulariy advantageous for the production of ethylene homopolymers and ethylene/a-olefin copolymers having high levels of long chain branching. The use of the catalysts of the present invention in continuous polymerization processes, especially continuous, solution polymerization processes, allows for elevated reactor temperatures which favor the formation of vinyl terminated polymer chains that may be incorporated into a growing polymer, thereby giving a long chain branch. The use of the present catalyst compositions advantageously allows for the economical production of ethylene/a-olefin copolymers having processability similar to high pressure, free radical produced low density polyethylene.
The present catalyst compositions may be advantageously employed to prepare olefin polymers having improved processing properties by polymerizing ethylene alone or ethylene/a-olefin mixtures with low levels of a"H" branch inducing SUBSTITUTE SHEET (RULE 26) diene, such as norbomadiene, 1,7-octadiene, or 1,9-decadiene. The unique combination of elevated reactor temperatures, high molecular weight (or low melt indices) at high reactor temperatures and high comonomer reactivity advantageously allows for the economical production of polymers having excellent physical properties and processability. Preferably such polymers comprise ethylene, a C3-20 a-olefin and a "H"-branching comonomer. Preferably, such polymers are produced in a solution process, most preferably a continuous solution process.
The catalyst composition may be prepared as a homogeneous catalyst by addition of the requisite components to a solvent or diluent in which polymerization will be conducted. The catalyst composition may also 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 polyolefins. In an preferred embodiment, a heterogeneous catalyst is prepared by reacting an inorganic compound, preferably a tri(C,.4 alkyl aluminum compound, with an activating cocatalyst, especially an ammonium salt of a hydroxyaryl(trispentafluoro-phenyl)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.
When prepared in heterogeneous or supported form, the catalyst composition is employed in a slurry or gas phase polymerization. As a practical limitation, slurry polymerization takes place in liquid diluents in which the polymer product is substantially insoluble. Preferably, the diluent for slurry polymerization is one or more hydrocarbons with less than 5 carbon atoms. If desired, saturated hydrocarbons such as ethane, propane or butane may be used in whole or part as the diluent.
Likewise the a-olefin monomer or a mixture of different a-olefin monomers may be used in whole or part as the diluent. Most preferably at least a major part of the diluent comprises the a-olefin monomer or monomers to be polymerized.
At all times, the individual ingredients as well as the recovered catalyst components must be protected from oxygen and moisture. Therefore, the catalyst SUBSTITUTE SHEET (RULE 26) components and catalysts must be prepared and recovered in an oxygen and moisture free atmosphere. Preferably, therefore, the reactions are performed in the presence of an dry, inert gas such as, for example, nitrogen.
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 therefrom.
Without limiting in any way the scope of the invention, one means for carrying out such a polymerization process is as follows: In a stirred-tank reactor, the monomers to be polymerized are introduced continuously together with solvent and an optional chain transfer agent. The reactor contains a liquid phase composed substantially of monomers together with any solvent or additional diluent and dissolved polymer. If desired, a small amount of a "H"-branch inducing diene such as norbomadiene, 1,7-octadiene or 1,9-decadiene may also be added. Catalyst and cocatalyst are continuously introduced in the reactor liquid phase. The reactor temperature and pressure may be controlled by adjusting the solvent/monomer ratio, the catalyst addition rate, as well as by cooling or heating coils, jackets or both. The polymerization rate is controlled by the rate of catalyst addition. The ethylene content of the polymer product is determined by the ratio of ethylene to comonomer in the reactor, which is controlled by manipulating the respective feed rates of these components to the reactor. The polymer product molecular weight is controlled, optionally, by controlling other polymerization variables such as the temperature, monomer concentration, or by the previously mention chain transfer agent, such as a stream of hydrogen introduced to the reactor, as is well known in the art. The reactor effluent is contacted with a catalyst kill agent such as water. The polymer solution is optionally heated, and the polymer product is recovered by flashing off gaseous monomers as well as residual solvent or diluent at reduced pressure, and, if necessary, conducting further devolatilization in equipment such as a devolatilizing extruder. In a continuous process the mean residence time of the catalyst and polymer in the reactor generally is from about 5 minutes to 8 hours, and preferably from 10 minutes to 6 hours. By using a catalyst that incorporates large amounts of hindered monovinyl monomer, hindered monovinyl homopolymer formed from residual quantities of the monomer are substantially reduced Ethylene homopolymers and ethylene/a-olefin copolymers are particularly suited for preparation according to the invention. Generally such polymers have densities from 0.88 to 0.96 g/ml. Typically the molar ratio of a-olefin comonomer to SUBSTITUTE SHEET (RULE 26) ethylene used in the polymerization may be varied in order to adjust the density of the resulting polymer. When producing materials with a density 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. In the above polymerization process hydrogen has been found to effectively control the molecular weight of the resulting polymer. Typically, the molar 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 0.02 and may even be less than 0.01.
EXAMPLES
The skilled artisan 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 construed as limiting. Unless stated to the contrary all parts and percentages are expressed on a weight basis. The term "ovemight", if used, refers to a time of approximately 16-18 hours, the temn "room temperature", refers to a temperature of about 20-25 C, and the tenn "mixed alkanes" refers to a commercially obtained mixture of C6.8 aliphatic hydrocarbons available under the trade designation Isopar E , from Exxon Chemicals Inc.
'H (300 MHz) and13C NMR (75 MHz) spectra were recorded on a VarianTm XL-300 spectrometer. 'H and13C 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 columns charged with activated alumina and a purifying catalyst (Q-5 available from Englehardt Chemicals Inc.) The compounds BCI3-SMe2, BBr3-SMe2r B(NMe2)3, n-BuLi were all used as purchased from Aldrich. The compound TiCl3(THF)3 was prepared as described in the literature. All syntheses were performed under'dry nitrogen or argon atmospheres using a combination of glove box and high vacuum techniques.

Example 1 Dichloro-[1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane]
titanium Me N
Me / N `B~ CI
M(a 11,,,,. . N B
ci Me/ ~

v 1 A) Preparation of Chlorobis(dimethylamido)borane, (modification of Chavant, P. Y.;
Vaultier, M. J. Organomet. Chem. 1993, 455, 37-46) BCI3-SMe2 (62.000 g, 345.78 mmol) and B(NMe2)3 (98.921 g, 691.56 mmole) were stirred together at room temperature ovemight 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).
'H NMR (C6D6): S 2.49 (s, 12 H). 13C NMR (C6D6): S 39.86.
1 B) Preparation of Tetrakis(dimethylamido)diborane (modification of Noth, H;
Meister, W. Z. Naturforsch., 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 tumed 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): S 2.74 (s, 24 H). 13C NMR (C6D6): S 41.34.
1 C) Preparation of Bis(dimethylamido)diborondichloride (modification of Noth, H;
Meister, W. Z. Naturforsch., Teil B 1962, 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 SUBSTITUTE SHEET (RULE 26) 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 (CsD6): S 2.40 (s, 6 H), 2.50 (s, 6 H). 13C NMR (C6D6): S 37.62, 41.78.
1 D) Preparation of 2,6-Diisopropylaniline, 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-diisopropylaniline (10.0 g, 56.4 mmol) in hexane (100 ml). This mixture was allowed to stir for 3 hours during which time a white precipitate formed.
After the reaction period the mixture was filtered and the white salt washed with hexane and dried under vacuum and used without further purification or analysis (9.99 g, 96.7 percent).
1 E) Preparation of 1,2-Bis(2,6-diisopropylanilide)-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-diisopropylaniline, lithium salt (4.77 g, 26.0 mmol) in diethylether (50 ml) at 0 C. This mixture was then allowed to stir ovemight 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): S 0.9-1.4 (br m, 24 H), 2.3 (s, 6 H), 2.8 (s, 6 H), 3.7 (s, H), 7.0 (br s, 6 H).
1 F) Preparation of 1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane, dilithium salt 1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane (1.82 g, 3.95 mmol) 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 ovemight.
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 (1.69 g, 90.4 percent yield).
1 G) Preparation of Dichloro-[1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diboranejtitanium 1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane, dilithium salt (0.60 g, 1.27 mmol) in THF (20 mi) 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 SUBSTITUTE SHEET (RULE 26) 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 ovemight resulted in the formation of orange X-ray quality crystals (0.156 g, 21.3 percent yield).
'H NMR (C6Ds): S 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-diisopropylanilide)-1,2-bis(dimethylamido)diborane]
titanium (altemated 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 ref lux 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): 8 2.49 (s, 12 H). 13C NMR (C6Ds): 839.86.
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 tumed 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): 8 2.73 (s, 24 H). 13C NMR (C6Ds): 6 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).

SUBSTITUTE SHEET (RULE 26) 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 (CgDs): S 2.40 (s, 6 H), 2.50 (s, 6 H). 13C NMR (C6D6): 837.62, 41.78.
2E) Preparation of 2,6-Diisopropylaniline, 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-diisopropylaniline (10.00 g, 56.40 mmol) in hexane (100 ml). This mixture was allowed to stir for 3 hours during which time a white precipitate formed. After the reaction period 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-diisopropylanilide)-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-diisopropylaniline, lithium salt (4.765 g, 26.01 mmol) in diethylether (50 ml) at 0 C. This mixture was then allowed to stir ovemight 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-ds): S 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). 13C NMR (toluene-d8): S 22.51, 24.03 (br), 28.17, 36.82, 42.67, 123.19, 124.78, 140.71, 145.02 (br). MS(El): m/z 460.4025 (M-H)+, calcd. (M-H)+
460.4026.
2G) Preparation of 1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane, dilithium salt.
1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane (1.820 g, 3.950 mmol) was stirred in 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 ovemight.
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).

SUBSTITUTE SHEET (RULE 26) 'H NMR (THF-d8): S 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, 3JHH= 7.5 Hz, 2 H), 6.73 (d, 3JHH= 7.5 Hz, 4 H). 13C NMR (THF-d8): S 24.88, 25.34, 28.00, 40.91, 114.40, 121.95, 137.21, 158.76.
2H) Preparation of Dichioro-[1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane]titanium.
1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane, dilithium salt (0.600 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 -ovemight resulted in the formation of orange X-ray quality crystals (0.156 g, 21.3 percent yield). The ORTEP crystal structure (not necessarily to scale) based on X-ray analysis is found in Figure 1.
'H NMR (toluene-d8): S 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). 13C
NMR
(toluene-de): S 24.94, 24.67, 29.48, 39.33, 42.93, 124.08 (br), 17.23, 150.64.
MS(El):
m/z 578.2789 (M)+, calcd. (M)'' 578.2781. Anal. Calcd. For C2aH4sB2N2TiCI2: C, 58.07;
H, 8.01; N, 9.67. Found: C, 8.28; H, 8.20; N, 9.42.

Example 3 Dimethyl [1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane]
titanium Dichloro-[1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane]
titanium (Example 2) (0.272 g, 0.470 mmol) 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 (CsD6): 6 1.05 (s, 6 H), 1.21 (d, 3JHH = 6.9 Hz, 16 H), 1.32 (d, 3JHH =
6.3 Hz, 16 H), 2.19 (s, 6 H), 2.69 (s, 6 H), 3.58 (br, 2 H), 7.0-7.2 (m, 6 H). 13C NMR
(C6D6): 8 24.06, 24.83, 29.31, 39.58, 42.93, 57.38, 123.97, 125.18, 139.5 (br), 149.45.

SUBSTITUTE SHEET (RULE 26) Example 4 Dibenzyl [1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethy{amido)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-diisopropylanilide)-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 ovemight 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-d8): S 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, 3JHH= 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): S 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 rac-diisopropylamidoborane-bis-il5-(2-methyl-4-phenylinden-1-yl)zirconium 114-1,4-diphenyl-1,3-butadiene Ph (iPr)2N-B Zr-Ph 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 ovemight at room temperature. The mixture was filtered, the residue was SUBSTITUTE SHEET (RULE 26) 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, 0.1 mm) to give 9.2g (51 percent) of product as a colorless liquid.
'H NMR (C6D6): S 0.95 (d, 12 H), 3.63 (broad multiplet, 2 H).
513) 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 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 rao-diisopropylaminoborane-bis-ri5- (2-methyl-4-phenyl indenyl)zirconium ri4-1,4-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. The ORTEP crystal structure (not necessarily to scale) based on X-ray analysis is found in Figure 2.
'H NMR (C6D6): S 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.

SUBSTITUTE SHEET (RULE 26) 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 ovemight 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). "B NMR (115 MHz, CDC13) 29.4. MS
(El,, m/e (intensity)): 181 (M+, 5), 166 (43), 124 (61), 43 (100) 6B) Diisopropylamidobis(cyclopentadienyl) borane To a solution of the above product (0.39 g, 2.1 mmol) in THF (5 ml) at -78 C
was added dropwise a solution of lithium cyclopentadienide (0.31 g, 2.1 mmol) in THF
(10 ml) at -78 C. The mixture was slowly warmed to room temperature and stirred ovemight 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.
13B NMR (115 MHz, C6D,) d 39.8 (major), 30.4 (minor). MS (El, m/e (intensity)): 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 (intensity)): 211 (M+, 24), 196 (100), 154 (22).
6C) Dilithium diisopropylamidoboryldicyclopentadienide To a solution of the above product (0.61 g, 2.53 mmol) in THF (7 ml) at -78 C
was added lithium diisopropylamide (5.57 mmol, prepared in situ from diisopropylamine (0.780 ml, 5.57 mmol) and BuLi (2.50 M, 2.23 ml, 5.57 mmol).
The mixture was warmed to room temperature and stirred for 2 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 (NCHCHa), 49.3 (NCH), 104.4, 111.9 "B NMR (115 MHz, THF-d8) d 44.6 6D) Diisopropylamidoboranebis(cyclopentadienyl)zirconium dichloride SUBSTITUTE SHEET (RULE 26) 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 suspension of ZrCl4 (0.69 g, 2.95 mmol) in Et20 (15 ml) at -78 C. The resulting mixture was stirred ovemight at room temperature to give an yellowish suspension. 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). 13C NMR (100 MHz, CDCI3) d 24.6, 49.6, 111.4, 125.7. 13B NMR (115 MHz, CDCI3) 5 37.6. HRMS (EI), calculated for C16H22BNC12Zr: 399.0269, found: 399.0272.

Example 7 Preparation of ineso-diisopropylamidoboranebis(inden-1-yl)zirconium dichloride 7A) Diisopropylamidobis(inden-1-yl)borane To a solution of diisopropylamidoboron dichloride (Example 3, step A)) (1.10 g, 6.0 mmol) in THF (10 mi) 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 ovemight 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:
"B NMR (115 MHz, C6D,) d 41.4. MS (El, m/e (intensity)): 341 (M+, 8), 226 (100). HRMS (EI), calculated for C24H28BN C24H2eBN: 341.2315, found: 341.2310 7B) Meso-Diisopropylamidoboranebis(inden-1-yl)zirconium dichloride To a suspension 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 mmol) and BuLi (2.50 M, 2.62 mmol). The mixture was stirred over night at room temperature to give an orange suspension. 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, about 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, CDCI3) 1.54(d, 6H, J= 6.6 Hz), 1.57 (d, 6H, J = 6.8 Hz), 4.27 (m, 2H, NCH), 5.91 (d, 2H, J3.0 Hz), 6.9 (m, 4H), 7.17 (t, 2H, J= 7.6 Hz), 7.31 SUBSTITUTE SHEET (RULE 26) (dd, 2H, J= 8.3, 3.6 Hz), 7.53 (d, 2H, J = 8.6 Hz). 13C NMR (75 MHz, CDCI3) 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 (EI), calculated for C24H26BNC12Zr:
499.0582, found, 499.0606. MS (El, m/e (intensity)): 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 mi).
The resulting solution was heated to 65 C and stirred for 2 hr to give a bright red solution. The product consisted 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 (EI), calculated for C28H38BN3Zr: 517.2206, found, 517.2217. MS (El, m/e (intensity)): 517 (M+, 20), 471 (45), 429 (100), 330 (24), 226 (70) Example 9 Rao-Diisopropylamidoboranebis(inden-l-yl)zirconium dichloride To a solution of rac-diisopropyfamidoboranebis(inden-1-yl)zirconium bis(dimethylamide) (0.50 g, 0.96 mmol) in toluene (35 ml) at room temperature was added trimethyhisilyl chloride (2.0 ml, 15.76 mmol). The solution was stirred for 8 h at room temperature to give an orange suspension. 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, CDCf3) 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.

SUBSTITUTE SHEET (RULE 26) HRMS (EI), calculated for C24H2gBNCI2Zr: 499.0582, found, 499.0606. MS (El, m/e (intensity)): 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 raa(diisopropylamidoborane)bis(tetrahydroinden-l-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 suspension. CH2CI2 (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, CsDs) d 1.06 (d, 12H, J= 6.6 Hz), 1.33 (m, 2H), 1.47 (m, 2H), 1.92 (m, 4H), 2.05 (t, 1 H, J 4.8 Hz), 2.09 (d, 1 H, J = 5.0 Hz), 2.34 (m, 2H), 2.53 (t, 1 H, J = 5.3 Hz), 2.56 (t, 1 H, 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). 13C NMR (100 MHz, C6D6) d 23.0, 23.6, 24.4, 24.7, 24.8, 27.0, 49.6, 109.7, 121.6, 124.2, 136.1. "B NMR (115 MHz, CsDs) d 39.2 ppm. HRMS (EI) Calculated for C24H34"BNC12Zr 507.1208, found 507.1198 Examole 11 Preparation of raoo-N,N-diisopropylamidoborane-bis-ri5- (2-methyl-4-naphthyl indenyl) zirconium rl -1,4-diphenyl-1,3-butadiene.
o ,oH~ O

(iPr)2N-B `Zr' C,oH~ =
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 SUBSTITUTE SHEET (RULE 26) 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.
11 B) Preparation of N,N-diisopropylamino bis(2-methyl-4-naphthylindenyl) borane To a solution of N,N-diisopropylaminoboron dichloride (0.309 g, 1.70 mmole) in 25 mi of THF at room temperature was slowly added dropwise a 10 mi 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).
11 C) Preparation of rao-N,N-diisopropylaminoborane-bis-rt5- (2-methyl-4-naphthyl indenyl) zirconium rt -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 (CsDs): S 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 rao-1,2-bis(dimethylamidodiborane)bis(2-methyl-4-phenylinden-l-yl)zirconium ri4-1,4-diphenyl-1,3-butadiene Ph Me2N , g I Zr"
Me2N -B

Ph SUBSTITUTE SHEET (RULE 26) 12A) Preparation of 1,2-Bis(2-methyl-4-phenylinden-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 ovemight 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) ovemight. 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 rao-[1,2-Bis(dimethylamido)-1,2-bis(2-methyl-4-phenylindene)diborane]zirconium( trans, trans-l,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 ovemight. 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). 13C NMR (C6D6): S 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 rao-diisopropylamidoborane-bis-ri5-(2-methyl-4-phenylinden-1-yl)hafnium rt4-1,4-diphenyl-1,3-butadiene SUBSTITUTE SHEET (RULE 26) O h (iPr)2N-B Hf-Ph 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 mmot, 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 ovemight 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-l-yl)2Hf(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 rac- 'Pr2NB(2-Me-4-Ph-inden-1-yl)2Hf(1,4-diphenyl-1,3-butadiene) was accomplished by soxhlet extraction using hexane.
After the hexane extract becomes colorless the thimble was removed and dried, yielding 0.042 g of pure rac- 'Pr2NB(2-Me-4-Ph-inden-1-yl)2Hf(1,4-diphenyl-1,3-butadiene) as determined by'H and13C NMR spectroscopic analysis.
'H NMR (C6D6): S 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 rao-diisopropylamidoborane-bis-ri5-(2-methyl-4-phenylinden-1-yl)zirconium ri4-1,4-diphenyl-1,3-butadiene SUBSTITUTE SHEET (RULE 26) h iPr)2N Zr, Ph =

In a glove box, diisopropylamidobis(2-methyl-4-phenyiinden-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 rao-{'Pr2NC(N'Pr)2)borane-bis-0 5- (2-methyl-4-phenylindenyl) zirconium 04-1,4-diphenyl-1,3-butadiene.

Ph O
(iPr)N
(iPr)ZNC' Zr, (iPr)N
Ph =
15A) Preparation of'Pr2NC(N'Pr)2)boron dichloride.
Diisopropylcarbodiimide (1.178 g, 9.33 mmole) was dissolved in 20 ml of toluene, cooled to 0 C, 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 -C) of boron trichloride (9.33 ml, 9.33 mmole) and allowed to warm to room temperature ovemight.
The solution was filtered, and solvents were removed under reduced pressure to yield 2.3 g (97 percent) of light yellow oil.

SUBSTITUTE SHEET (RULE 26) 'H NMR (CsDs): 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) {'Pr2NC(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 in vacuo to give a light yellow solid (0.533 g, 85 percent).
15C) Preparation of rao-{'Pr2NC(NrPr)2}borane -bis-^5- (2-methyl-4-naphthyl indenyl) zirconium 04-1,4-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 (0Ø328 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.
Volatile components were removed under reduced pressure to yield 0.382 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-butadiene)bis(triethylphosphine)zirconium dichforide (0.084 g, 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): 8 7.6-6.7, (mm, 26 H); 5.55 (s, 2H); 4.05-3.90(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 racdimethylamidoborane-bis-rl5-(2-methyl-4-phenylinden-1-yl)zirconium rt4-1,4-diphenyl-1,3-butadiene SUBSTITUTE SHEET (RULE 26) h (Me)2N-B Zr;
Ph 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): S 2.31 (6 H). 13C NMR (C6D6): S 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 resutted 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) ovemight.
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-l,4-diphenyl-1,3-butadiene).
Dimethylamido-bis(2-methyl-4-pheny-Iindenyl)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 ovemight. 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 SUBSTITUTE SHEET (RULE 26) 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): S 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, 3JHH= 7.2 Hz, 4 H), 6.8-7.4 (m, 12 H), 7.43 (d, 3JHH= 8.4 Hz, 2 H).
13C NMR (C6D6): S 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(El): m/z 759.2635 (M-H)+, calcd. (M-H)+ 759.2610.
Example 17 bis(trimethylsilyl)amido(rl-fluoren-9-yi)(rt-cyclopentadienyi)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 ovemight 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): S 0.45 (s, 18H), 4.41 (s, 1 H), 7.34 (dt, 2H, J =
7.4, 1.1 Hz), 7.42 (t, 2H, J = 7.3 Hz), 7.49 (d, 2H, J = 7.6 Hz), 7.87 (d, 2H, J =
7.4 Hz).
13C NMR (100 MHz, CDCI3) S 4.6, 121.0, 125.4, 127.2, 127.3, 143.0, 145.9. "B
NMR
(115.5 MHz, CDCI3,) S 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 bistrimethylsilyamido(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 SUBSTITUTE SHEET (RULE 26) 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): 6 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). '3C NMR (100 MHz, C6D6,) S 5.1, 43.4, 120.6, 125.8, 126.7, 127.2, 132.2, 139.5, 142.9, 143.1, 147.4. "B NMR (115.5 MHz, C6D6) 5 51.6. HRMS (EI) calculated for C23H29BNSi, (M-CH3), 386.1932; found, 386.1945.
17C)) bis(trimethylsilyl)amidoborane(rf-cyclopentadienyl)(ri-fluoren-9-yl)zirconium dichloride A solution of lithium diisopropylamide (prepared in situ from iPr2NH (0.54 ml, 3.84 mmol) and BuLi (2.5 M hexane, 1.61 mil, 4.03 mmol)) in THF (10 ml) was added to a solution of bis(trimethylsifyl)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 ovemight to give a dark red solution. Volatile components were removed to give an orange solid which was then dissolved in toluene (15 mi). The toluene solution was added to a suspension of ZrCI4 (0.40 g, 1.9 mmol) in toluene (8 ml) at -78 C. The mixture was warmed to room temperature and stirred ovemight 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) 84.8,5.9,105.3,121.4,122.9,124.4,125.4,125.7,129.1,143,0. 11B NMR (115.5 MHz, CDC13) 5 48.2. HRMS (EI) calculated for C24H3oBNSi2CI2Zr: 559.0434;
found, 559.0443.

Example 18 diisopropylamidoborane(,n-cyclopentadienyi)(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 SUBSTITUTE SHEET (RULE 26) 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.
'H NMR (400 MHz, CDCI3): S 1.36 (br, 6H), 1.79 (br, 6H), 4.41 (br, 1 H), 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) S 24.5 (br), 43.2 (br), 48.5 (br), 120.2, 124.4, 126.4, 126.9, 141.1 (br), 146.9. "B NMR (115.5 MHz, CDC13) S 37.2. HRMS (EI) Calculated for C,9H23BNCI, 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.
Volatiles were removed to give the product (2.11 g, 62 percent) as a yellow solid.
HRMS (EI), Calculated for C24H28BN, 341.2315, found, 341.2329.
18C) Preparation of diisopropylamidoborane(rl-cycfopentadienyl)(ri-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(trimethylsilyl)amido(9-fluorenyl)boron. The crude reaction mixture from this reaction was extracted with toluene and filtered. The solution was concentrated, pentane was added and cooled to -78 C 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, 1 H, J = 6.6 Hz), 5.30 (t, 2H, J = 2.4 Hz), 6.38 (t, 2H, J = 2.4 Hz), 7.05 (d, 2H, J = 8.1 Hz), 7.12 (t, 2H, J = 7.5 Hz), 7.46 (t. 2H, J = 7.5 Hz), 7.92 (d, 2H, J = 8.5 Hz). '3C NNIR (90 MHz, CDC13) S
24.2, 25.4, 49.1, 49.8, 106.9, 122.2, 123.2, 125.4, 125.8, 129.0, 147.9, 157. 1. "B
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(rl-inden-1-yl)zirconium bis(dimethylamide) SUBSTITUTE SHEET (RULE 26) 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): S 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) S 56.8. HRMS (EI) calculated for C24H32BNSi2i 401.2166; found, 401.2182. EA, Calculated for C24H32BNSi2r 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-1-yi) (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 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): S 0.26 (s. 18H), 2.53 (s, 12H), 5.95 (d, 2H, J = 2.9 Hz), 6.64 (d, 2H, J = 2.9 Hz), 6.68 (t, 2H, J = 7.5 Hz), 6.95 (t, 2H, J = 7.6 Hz), 7.30 (d, 2H, J = 8.5 Hz), 7.45 (d, 2H, J = 8.8 Hz). 13C NMR (100 MHz, C6D6) 6 5.6, 47.9, 105.1, 111.5, 122.2, 122.9, 124.2, 126.4, 128.5. "B NMR (115.5 MHz, C6D6) S
50.3.
HRMS (EI) calculated for C28H42BN3Si2Zr, 577.2057; found, 577.2061.

Example 20 Bis(trimethyl)silylamidobis(rl-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) ovemight 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, CfiD6): S 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). 13C NMR
(100 MHz, C6D6) S 5.3, 112.8, 113.0, 123.6, 126.5, 127.1, 127.8, 132.1. "B NMR
(115.5 MHz, C6D6) S 48.5. HRMS (EI) calculated for C24H3oBNSi2CI2Zr, 559.0434; found, 559.0432.

SUBSTITUTE SHEET (RULE 26) Example 21 Preparation of rao-diisopropylamidoborane-bis-^5- (2-isopropyf-4-phenyl indenyl)zirconium ^4-1,4-diphenyi-1,3-butadiene Q Ph ~ Ph N-B Zr Ph Ph 21 A) 2-Isopropyl-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 (100mI) 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 moming 100 ml of 1 N ammonium chloride was added. The solution was diluted with ether (200 ml) and the organic layer was washed with brine, dried over Na2SO4i 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 ovemight.
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 SUBSTITUTE SHEET (RULE 26) 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 Na2SO4, 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-Isopropyl-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 ovemight, 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 Na2SO4, 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 (0.5 g) 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 and the organic layer was separated, dried over Na2SO4, 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 cold under an inert atmosphere until ready for further conversion.
'H-NMR (CDCI3): ^^^1.18 (d, 6H), 2.74 (sept, 1H), 3.39 (s, 2H), 6.53 (s, 1 H), 7.09-7.55 (m, 8H).
21 B) Lithium 2-isopropyl-4-phenylindenide To a toluene solution (25 ml) of 2-isopropyl-4-phenylindene (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 ovemight. The toluene was removed under reduced pressure. Hexane (20 ml) was added and removed under reduced pressure then added again (50 ml). The mixture was stirred for 1 h then SUBSTITUTE SHEET (RULE 26) 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 (de-THF): ^^^1.27 (d, 6H), 3.02 (sept, 1 H), 5.84 (s, 1 H), 6.06 (s, 1 H), 6.42-6.51 (m, 2H), 7.15 (t, 1 H), 7.18 (d, 1 H), 7.26 (t, 2H), 7.82 (d, 2H). 13C-NMR
(de-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.
21 C) N,N-diisopropylamido bis(2-isopropyl-4-phenylindenyl) borane To 25 ml toluene solution of N,N-diisopropylamidoboron dichloride (0.501g, 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).
21 D) rao-diisopropylamidoborane-bis-^5-(2-isopropyl-4-phenyl indenyl)zirconium ^4-1,4-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 C 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): 5 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).

SUBSTITUTE SHEET (RULE 26) Example 22 Supported raadiisopropylamidoborane-bis-,q5-(2-methyl-4-phenylinden-1-yl)zirconium 11 -1,4-diphenyl-1,3-butadiene In a glass flask, 0.922 ml of a toluene solution of methyldi(octyl)ammonium hydroxyphenyltris(pentafluorophenyl)borate (amounting to 0.070 mmoles based on boron) and 0.110 ml of a 1.9 M toluene solution of triethyl aluminum (0.058 mmoles) were added along with 0.290 mi additional toluene. The mixture was stirred for minutes on a mechanical shaker. About one half (0.550 ml) of the resulting solution was added to a flask containing 0.500 g of thoroughly dried silica (Grace-Davison 948 silica, heated 250 C, 4 h). The mixture was shaken by hand to break-up clumps and then mechanically agitated for an additional 10 minutes. Next 8 ml of mixed hexanes was added to form a slurry, which was mechanically stirred for an additional minutes. To this mixture, 3.5 ml of a 0.005 M toluene solution of rac-diisopropylamidoborane-bis-ri5-(2-methyl-4-phenylinden-1-yl)zirconium rt'-1,4-diphenyl-1,3-butadiene (Example 14) was added. The mixture was agitated 2 h on the mechanical shaker, filtered on a glass frit, washed (3x) with 10 ml mixed hexanes and dried under reduced pressure.
The resulting blue colored, dried, supported catalyst was analyzed by neutron activation for zirconium content and found to contain 31.8 mole zirconium/g formulated supported catalyst.
Solution Polyethylene Polymerization Mixed hexanes and 1-octene were purified by sparging with purified nitrogen followed by passage through columns containing alumina (A-2, available from LaRoche Inc.) and Q5 reactant (available from Englehard Chemicals Inc.) at 50 psig using a purified nitrogen pad. All transfers of solvents and solutions described below were accomplished using a gaseous pad of dry, purified nitrogen or argon.
Gaseous feeds to the reactor were purified by passage through columns of A-204 alumina (available from LaRoche Inc.) and Q5 reactant. The aluminas were previously activated by treatment at 375 C with nitrogen and Q5 reactant was activated by treatment at 200 C with 5 percent hydrogen in nitrogen.
Batch reactor polymerizations were conducted in a two liter Parr reactor equipped with an electrical heating jacket, intemal serpentine coil for cooling, and a bottom drain valve. Pressures, temperatures and block valves were computer monitored and controlled. Mixed alkanes solvent (about 740 g) and 1 -octene (118 g) were measured in a solvent shot tank fitted with a differential pressure transducer or weigh cell. These liquids were then added to the reactor from the solvent shot tank.

SUBSTITUTE SHEET (RULE 26) The contents of the reactor were stirred at 1200 rpm. Hydrogen was added by differential expansion (0 25 psi, 170 kPa) from a 75 mi shot tank initially at 300 psig (2.1 Mpa). The contents of the reactor was then heated to the desired run temperature under 500 psig (3.4 Mpa) of ethylene pressure. The catalyst composition (as a 0.0050 M solution in toluene)- and cocatalyst were combined in the desired ratio in the glove box and transferred from the glove box to the catalyst shot tank through 1/16 in (0.16 cm) tubing using toluene to aid in the transfer.
The catalyst tank was then pressurized to 700 psig (4.8 Mpa) using nitrogen. After the contents of the reactor had stabilized at the desired run temperature of 140 C, the catalyst was injected into the reactor via a dip tube. The temperature was maintained by allowing cold ethylene glycol to pass through the intemal cooling coils. The reaction was allowed to proceed for 15 minutes with ethylene provided on demand. Additional injections of catalyst composition prepared and injected in the same manner were employed where indicated. The contents of the reactor were then expelled into a 4 liter nitrogen purged vessel and quenched with isopropyl alcohol.
Approximately 10 ml of a toluene solution containing approximately 67 mg of a hindered phenol antioxidant (IrganoxT"" 1010 from Ciba Geigy Corporation) and 133 mg of a phosphorus stabilizer (IrgafosTM 168 from Ciba Geigy Corporation) were added.
Volatile materials were removed from the polymers in a vacuum oven that gradually heated the polymer to 140 C ovemight and cooled to at least 50 C prior to removal from the oven. After completion of the polymerizaiton, the reactor was washed with 1200 ml of mixed hexanes solvent at 150 C before reuse. Results are contained in Table 1.
Table 1 Catalyst/ T
cocatalyst ( C) Yield Density* MMI**
Run Catalyst cocatalyst ( moles) (g) g/ml dg/min.) 1 Ex. 2 MATB 5/5 140 31.5 0.892 436 2 " " " " 26.7 0.901 186 3 " MABU2 " 18.3 0.891 199 4 " TPB3 " 5.3 0.892 500+
5 TPA4 5/20 " 10.2 0.896 500+
6 Ex. 3 MATB 5/5 " 17.1 0.902 33 7 " " " " 6.3 0.908 500+
8 " MABU2 " 0.3 - -SUBSTITUTE SHEET (RULE 26) 9 TPB3 4.5 - -TPA4 5/20 " 0.7 - -11 Ex.17 MAO 1/1000 " 142.1 - 2.8 12 0.75/750 " 133.4 - 1.9 13 Ex.18 1/1000 " 130.8 0.90 1.8 14 " 0.5/500 120.6 Ex.20 164.9 " -density is determined by displacement technique using methylethylketone micromelt index technique, calibrated using standards of known melt index.
' methyidi(octadecy!)ammonium tetrakis(pentafluorophenyl)borate (this ammonium cation is 5 derived from a mixture of amines available commercially as methylbistallowamine).
2. methylbis(octadecyl)ammonium bis(tris(pentafluorophenyl)aluminane)undecvlimidazolide (prepared according to U.S. Patent No. 6,395,671) '* tris(pentafluorophenyl)borane, (C6Fs)3B
10 ' tris(pentafluorophenyi)aluminane, (C6F5),AI
5. methylalumoxane availablE> from Albemarle Corp.
Solution Polvaropy,iene Polymerization The above reaction conditions were substantially repeated excepting about 15 625 g of mixed alkanes solvent and either 150 g of propylene (P) for homopolymer formation, or a mixture of 150 g propylene and 7 g ethylene (E) for copolymer formation were used. Hydrogen was added as a molecular weight control agent by differential pressure expansion from a 75 mi addition tank at about 17-25 psi (120-170 kPa). The reactor was heated to the polymerization temperature and the desired metal complex along with a cocatalyst, as dilute solutions in toluene, were mixed at an appropriate molar ratio, transferred to a catalyst addition tank, and injected into the reactor (three injections of 1 mole, 3 mole and 5 mole based on zirconium over about 30 minutes for run 16, two injections of 5}unole based on zirconium over about 20 minutes for nin 17, and a single addition for all other runs. Results are contained in Table 2.

Table 2 Catalyst/
cocatalyst mono T Time Yield Tm Mw Run Catalyst cocatalyst ( moles) mer (2C) (min.) (g) ( C) x10"3 16 Ex.1 MAO 9/9000 P 70 51 9.2 155.6 -17 Ex. 1 " 10/10,000 E/P " 58 10.3 145.9 -18 Ex. 5 MDAP2 1/1.25 P " 7 43.5 155.8 -19 Ex.5 MABU3 0.25/0.25 " " 29.8 155.7 357 20 Ex.13 " " " " 30 33.5 157.3 330 21 Ex.5 " 0.5/0.5 " 85 5 42.2 152.2 195 22 Ex.13 " 0.75/0.75 " " " 41.3 153.9 183 23 Ex.5 " 0.5/0.5 " 100 12.4 151.4 136 24 Ex.13 0.75/0.75 " " " 16.2 150.3 117 25 Ex.5 1.5/1.5 " 115 12 19.8 146.7 75 26 Ex.13 1.75/1.75 " " 10 19.4 147.4 69 27 Ex.5 2.5/25 " 130 11 12.7 143.2 48 28 Ex. 13 3.75/3.75 " " 17 16.4 142.0 15 29 Ex.17 MAO 6/6000 " 70 118.9 117 114 30 Ex.18 " " " " 107.9 112 111 31 Ex. 20 " " " " 126.6 108 -32 Ex. 16 MABU 0.75/0.75 " 90 15 96.4 152.7 -' methylalumoxane available from Albermarle Corp.
2. methyldi(octadecyl)ammoniumtris(pentafluorophenyl)(p-(diethylaluminoxyphenyl) borate (formed by reaction of triethylaluminum and methyidi(octadecyl)ammonium tris(pentafluorophenyl)(hydroxyphenyl) borate) 3. methylbis(octadecyl)ammonium bis(tris(pentafluorophenyl)aluminane)undecylimidazolide Slurry Pofymerization The previous reaction conditions were substantially repeated excepting a supported catalyst was employed, the temperature was between 20 C and 60 C, and no solvent was used. All feeds were passed through columns of alumina and a decontaminant (Q-5 catalyst available from Englehardt Chemicals Inc.) prior to SUBSTITUTE SHEET (RULE 26) introduction into the reactor. Catalyst and cocatalysts were handled in a glovebox containing an atmosphere of argon or nitrogen. A stirred 2.0 liter reactor was charged with about 500 g of propylene. Hydrogen was added by differential pressure expansion from a 75 ml addition tank at 40 psi (280 kPa). The reactor was adjusted to the initial polymerization temperature (25 QC) and a slurry of the supported catalyst composition (40 g, 1.27 mole Zr) in mixed hexanes was injected into the reactor.
The temperature was maintained at 25 gC for 20 minutes then increased to 60 C
over 6.5 minutes (2.8 minutes for run 33) and maintained at 60 4C for a total run time of 40 minutes.
Upon completion, the reactor contents were removed and about 10 ml of a toluene solution containing approximately 67 mg of a hindered phenol antioxidant (IrganoxTM 1010 from Ciba Geigy Corporation) and 133 mg of a phosphorus stabilizer (IrgafosTM 168 from Ciba Geigy Corporation) were added. The polymer was recovered by drying in a vacuum oven set at 140 C for about 20 hours. Results are contained in Table 3.
Table 3 Run Catalyst Zr ( mole) Yield(g) Tm Mw Mw/Mn (mg) ('C) x 10"3 32 Ex. 22 (40) 1.27 61.5 150 283 3.0 33 Ex. 22 (32) 1.02 47.4 - - -SUBSTITUTE SHEET (RULE 26)

Claims (15)

1. A Group 4 transition metal complex corresponding to one of the following formulas:

or a dimer thereof, wherein:
M is titanium, zirconium, or hafnium in the +4, +3, or +2 oxidation state;
Y1 and Y2 are independently a .pi.bonded anionic group, a .pi.-bonded cyclic group, a .pi.-bonded non-cyclic group or NR1, PR1, NR1 2 or PR1 2;
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 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. A metal complex according to claim 1 corresponding formula 4, 5, 6, 7, 8 or 9:

wherein M, Z, T, R1, Q and j are as defined in claim 1;
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; and R3 is independently hydrogen, a hydrocarbyl group, a trihydrocarbylsilyl group or a trihydrocarbylsilyihydrocarbyl group, said R3 having up to 20 atoms not counting hydrogen.
3. A metal complex according to 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 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.
4. A metal complex according to 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, suifido 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 unsaturation able to form an .eta.3-bond with M.
5. A metal complex according to 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 .pi.-complex with M.
6. A metal complex according to claim 3 corresponding to Formula 4a, 5a, 6a, 7a, 8a, or 9a, wherein the definitions of M, Z, R1, R2, and R3 are as defined 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 conjugated C4-20diene ligand that together with M forms a metallocyclopentene.
7. A metal complex according to claim 4 corresponding to Formula 4b, 5b, 6b, 7b, 8b, or 9b, wherein the definitions of M, Z, R1, R2, and R3 are as defined 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 .eta.3 bond with M.
8. A metal complex according to claim 5 corresponding to Formula 4c, 5c, 6c, 7c, 8c, or 9c, wherein the definitions of M, Z, R1, R2, and R3 are as defined in claim 5:

and 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 .pi.-complex with M.
9. A metal complex according to claim 6, 7 or 8 wherein Z is boron.
10. A metal complex according to claim 6 or 8 wherein Z is boron, and in formulas 4a, 4c, 7a or 7c, M is zirconium or hafnium and R' is methyl or isopropyl.
11. A metal complex according to claim 1 which is dimethylamidoborane-bis(.eta.5-cyclopentadienyl)zirconium dichloride, dimethylamidoboranebis(.eta.5-inden-1-yl)zirconium dichloride, dimethylamidoborane-bis(.eta.5-2-methyl-4-phenylinden-yl)zirconium dichioride, dimethytamidoborane-bis(.eta.5-2-ethyl-4-phenylinden-yl)zirconium dichioride, dimethylamidoborane-bis(.eta.5-2-isopropyl-4-phenylinden-1-yl)zirconium dichioride, dimethylamidoborane-bis(.eta.5-2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium dichioride, dimethylamidoborane-bis(.eta.5-3-t-butylinden-1-yl)zirconium dichloride, diisopropylamidoborane-bis(.eta.5-cyclopentadienyl)zirconium dichloride, diisopropylamidoboranebis(.eta.5-inden-1-yl)zirconium dichloride, diisopropylamidoborane-bis(.eta.5-2-methyl-4-phenylinden-1-yl)zirconium dichloride, diisopropylamidoborane-bis(.eta.5-2-ethyl-4-phenylinden-1-yl)zirconium dichloride, diisopropylamidoborane-bis(.eta.5-2-isopropyl-4-phenylinden-1-yl)zirconium dichloride, diisopropylamidoborane-bis(.eta.5-2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium dichloride, diisopropylamidoborane-bis(.eta.5-3-t-butylinden-1-yl)zirconium dichloride, diphenylamidoborane-bis(.eta.5-cyclopentadienyl)zirconium dichloride, diphenylamidoboranebis(.eta.5-inden-1-yl)zirconium dichloride, diphenylamidoborane-bis(.eta.5-2-methyl-4-phenylinden-1-yl)zirconium dichloride, diphenylamidoborane-bis(.eta.5-2-ethyl-4-phenylinden-1-yl)zirconium dichloride, diphenylamidoborane-bis(.eta.5-2-isopropyl-4-phenylinden-1-yl)zirconium dichloride, diphenylamidoborane-bis(.eta.5-2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium dichloride, diphenylamidoborane-bis(.eta.5-3-t-butylinden-1-yl)zirconium dichloride, dimethylamidoborane-bis(.eta.5-cyclopentadienyl)zirconium 1,4-diphenyl-1,3-butadiene, dimethylamidoboranebis(.eta.5-inden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, dimethylamidoborane-bis(.eta.5-2-methyl-4-phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, dimethylamidoborane-bis(.eta.5-2-ethyl-4-phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, dimethylamidoborane-bis(.eta.5-2-isopropyl-4-phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, dimethylamidoborane-bis(.eta.5-2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, dimethylamidoborane-bis(.eta.5-3-t-butylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, diisopropylamidoborane-bis(.eta.5-cyclopentadienyl)zirconium 1,4-diphenyl-1,3-butadiene, diisopropylamidoboranebis(.eta.5-inden-1-yl)zirconium 1,4-diphenyl-l,3-butadiene, diisopropylamidoborane-bis(.eta.5-2-methyl-4-phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, diisopropylamidoborane-bis(.eta.5-2-ethyl-4-phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, diisopropylamidoborane-bis(.eta.5-2-isopropyl-4-phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, diisopropylamidoborane-bis(.eta.5-2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zinronium 1,4-diphenyl-1,3-butadiene, diisopropylamidoborane-bis(.eta.5-3-t-butylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, diphenylamidoborane-bis(.eta.5-cyclopentadienyl)zirconium 1,4-diphenyl-1,3-butadiene, diphenylamidoboranebis(.eta.5-inden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, diphenylamidoborane-bis(.eta.5-2-methyl-4-phenylinden-1-yl)zirconium 1,4 diphenyl-1,3-butadiene, diphenylamidoborane-bis(.eta.5-2-ethyl-4-phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, diphenylamidoborane-bis(.eta.5-2-isopropyl-4-phenyiinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, diphenylamidoborane-bis(.eta.5-2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, or diphenylamidoborane-bis(.eta.5-3-t-butylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene.
12. A polymerization process comprising contacting one or more addition polymerizable monomers under polymerization conditions with a catalyst comprising one or more metal complexes as defined in any one of claims 1 to 11
13. The process of claim 12 wherein the catalyst additionally comprises one or more activating cocatalysts.
14. The process of claim 12 conducted under solution, slurry or high pressure polymerization conditions.
15. The process of claim 13 conducted under slurry polymerization conditions, wherein the catalyst additionally comprises an inert, particulated support.
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