BORON-BRIDGED 2-INDENYL METALLOCENE COMPLEXES FOR OLEFIN POLYMERIZATION

Abstract

I, II, III and IV,

##STR00001## wherein Y is a C.sub.1-C.sub.20 linear, branched or cyclic hydrocarbyl group, or a C.sub.6-C.sub.30 aryl or substituted aryl group; L is an electron-donating ligand; A is an element selected from Group 15 or 16; R is a C.sub.1-C.sub.30 alkyl, aryl, or substituted aryl group; n is an integer from 1 to 3; m is an integer from 1 to 4; B is a boron atom; M is selected from lanthanides or transition metals from group 3, 4, 5 or 6; X is an anionic ligand to M and z is the valence of M minus 2; and a catalyst comprising a 2-indenyl metallocene complex, a ligand precursor, a process for preparation of a ligand precursor, a process for preparation of olefin polymers in the presence of 2-indenyl metallocene complexes, articles comprising an olefin polymer, and methods of making the articles.

Claims

1. A mMetallocene complex selected from the group consisting of 2-indenyl complexes I, II, III and IV, ##STR00021## wherein Y is a C.sub.1-C.sub.20 linear, branched or cyclic hydrocarbyl group, or a C.sub.6-C.sub.30 aryl or substituted aryl group; L is an electron-donating ligand; A is an element selected from Group 15 or 16 of the Periodic System of the Elements; R is a C.sub.1-C.sub.30 alkyl, aryl, or substituted aryl group; n is the number of R groups and is an integer from 1 to 3; m is the number of carbon atoms in the hydrocarbyl group between A and B and is an integer from 1 to 4; B is a boron atom; M is a metal selected from lanthanides or transition metals from group 3, 4, 5 or 6 of the Periodic System of the Elements; X is an anionic ligand to M, and z is the number of X groups and equals the valence of M minus 2.

2. The niMetallocene complex according to claim 1, wherein the metal M is selected from the group consisting of Ti, Zr, Hf, V and Sm, and wherein X is selected from the group consisting of halogen (F, Cl, Br and I), a C.sub.1-C.sub.20 hydrocarbyl group or a C.sub.1-C.sub.20 alkoxy group.

3. The metallocene complex according to claim 1, wherein A is O, S, N or P.

4. The metallocene complex according to claim 1, wherein Y is a C.sub.6-C.sub.30 aryl or substituted aryl group.

5. The metallocene complex according to claim 1, wherein L is selected from pyridine, tetrahydrofuran, dimethylsulfide and trimethylphosphine.

6. The metallocene complex according to claim 5, wherein Y is a phenyl group; A is O, S, N or P; R is a C.sub.1-C.sub.30 alkyl, aryl, or substituted aryl group and n is the number of R groups and is an integer from 1 to 3; B is a boron atom; M is selected from the group consisting of Ti, Zr and Hf; X is Cl or a methyl group; and z is the number of X groups and equals the valence of M minus 2.

7. The metallocene complex according to claim 1, wherein the metallocene complex is immobilized on a support.

8. A catalyst comprising a metallocene complex according to claim 1 and a cocatalyst.

9. A ligand precursor selected from the group consisting of ligand precursors according to formulas V or VI, ##STR00022## wherein, Y is a C.sub.1-C.sub.20 linear, branched or cyclic hydrocarbyl group, or a C.sub.6-C.sub.30 aryl or substituted aryl group; A is an element selected from Group 15 or 16 of the Periodic System of the Elements; R is a C.sub.1-C.sub.30 alkyl, aryl, or substituted aryl group; n is the number of R groups and is an integer from 1 to 3; and B is a boron atom; with the exception of bis(2-indenyl)(diisopropylamino)borane.

10. A process for the preparation of a ligand precursor of formula V or VI according to claim 9, the process comprising activating Mg with 1,2-dibromoethane, reacting the activated Mg with 2-bromoindene to form a Grignard solution reacting the Grignard solution with Me.sub.3SnCl to form a compound according to formula VII and ##STR00023## reacting the compound according to formula VII with dichloroYB or dichloro(R.sub.nA)B to form the ligand precursor according to formula V or VI, wherein Y is a C.sub.1-C.sub.20 linear, branched or cyclic hydrocarbyl group, or a C.sub.6-C.sub.30 aryl or substituted aryl group; A is an element selected from Group 15 or 16 of the Periodic System of the Elements; R is a C.sub.1-C.sub.30 alkyl, aryl, or substituted aryl group; n is the number of R groups and is an integer from 1 to 3; and B is a boron atom.

11. A process for the preparation of olefin polymers the process comprising polymerizing one or more olefins, in the presence of the metallocene complex according to claim 1 and a cocatalyst.

12. The process according to claim 11, wherein a mixture of ethylene and at least one other olefin of 3 or more carbon atoms is used.

13. A polyolefin obtained by the process of claim 11.

14. (canceled)

15. An articles comprising an olefin polymer, that is prepared with a catalyst comprising a metallocene complex according to claim 1.

16. An article comprising an olefin polymer that is prepared with a catalyst comprising a metallocene complex according to claim 6.

17. The article of claim 16, wherein the olefin polymer is high density polyethylene.

18. The catalyst according to claim 8, wherein Y is a phenyl group; A is O, S, N or P; R is a C.sub.1-C.sub.30 alkyl, aryl, or substituted aryl group and n is the number of R groups and is an integer from 1 to 3; B is a boron atom; M is selected from the group consisting of Ti, Zr and Hf; X is Cl or a methyl group; and z is the number of X groups and equals the valence of M minus 2.

19. The ligand precursor according to claim 9, wherein Y is a phenyl group; A is O, S, N or P; R is a C.sub.1-C.sub.30 alkyl, aryl, or substituted aryl group and n is the number of R groups and is an integer from 1 to 3; B is a boron atom.

20. The process of claim 11, wherein Y is a phenyl group; A is O, S, N or P; R is a C.sub.1-C.sub.30 alkyl, aryl, or substituted aryl group and n is the number of R groups and is an integer from 1 to 3; B is a boron atom; M is selected from the group consisting of Ti, Zr and Hf; X is Cl or a methyl group; and z is the number of X groups and equals the valence of M minus 2.

21. The process of claim 11, wherein the at least one olefin is ethylene.

Description

FIGURE

[0100] FIG. 1 shows GPC data of polyethylenes prepared with two different catalysts according to the invention. The top diagram shows the GPC spectrum of the polyethylene produced with a catalyst comprising compound 3 (top) and while the bottom diagram shows the GPC spectrum of the polyethylene produced with compound 4 (bottom).

EXAMPLES

General Considerations

[0101] All manipulations were carried out under an atmosphere of dry, O.sub.2-free N2 employing an Innovative Technology glove box and a Schlenk vacuum-line. Tetrahydrofuran (THF), toluene, methylene chloride, hexane and pentane were purified with a Grubbs-type column system manufactured by Innovative Technology and dispensed into thick-walled Schlenk glass flasks equipped with Teflon-valve stopcocks. Pyridine was dried over the appropriate agents and distilled into the same kind of storage flasks. Anhydrous benzene (Alfa, 99.8%, packaged under argon) was purchased and used as received. Deuterated solvents were dried over the appropriate agents, vacuum-transferred into storage flasks with Teflon stopcocks and degassed accordingly (CDCl.sub.3, C.sub.6D.sub.6 and CD.sub.2Cl.sub.2). .sup.1H, .sup.11B, .sup.13C and .sup.31P NMR spectra were recorded at 25° C. Bruker 400 MHz spectrometers. Chemical shifts are given relative to SiMe.sub.4 and referenced to the residue solvent signal (.sup.1 H, .sup.13C). .sup.11B and .sup.31P resonances were referenced externally to (BF.sub.3.Et.sub.2O) and 85% H.sub.3PO.sub.4, respectively. Chemical shifts are reported in ppm and coupling constants as scalar values in Hz. ZrCl.sub.4(Me.sub.2S).sub.2, .sup.1TiCl4(THF).sub.2.sup.2 and TiCl.sub.4(Me.sub.2S).sub.2.sup.3 were prepared as reported in, respectively, Sassmannshausen, J. Organometallics 2000, 19, 482-489; Seenivasan, K.; Sommazzi, A.; Bonino, F.; Bordiga, S.; Groppo, E. Chemistry—a European Journal 2011, 17, 8648-8656 and Suren Lewkebandara, T.; McKarns, P. J.; Haggerty, B. S.; Yap, G. P. A.; Rheingold, A. L.; Winter, C. H. Polyhedron 1998, 17, 1-9. ZrCl.sub.4(THF).sub.2 (Strem) was purchased and used as received.

Example 1

Synthesis of trimethyl(1 H-inden-2-yl)stannane

[0102] ##STR00005##

[0103] A Schlenk flask was charged with a magnetic stir bar and Mg turnings (1.85 g, 77 mmol, 3.0 eq.) and flame-dried under vacuum. After cooling, the flask was purged to N.sub.2, anhydrous THF (15 mL) was added to just cover the turnings, and stirring was commenced. 1,2-dibromoethane (0.1 mL) was added as initiator, and a heat gun used to briefly reflux the contents, after which the flask was placed in a 25° C. water bath. In a separate flame-dried flask under N.sub.2 atmosphere, 2-bromoindene (5.0 g, 25.6 mmol, 1.0 eq.) was dissolved in 25 mL anhydrous THF. A cannula was then used to transfer this solution onto the activated magnesium turnings over 10 min, resulting in a red, opaque solution. After 1.5 h, GCMS analysis of an aliquot sample showed consumption of the 2-bromoindene. A separate flame-dried flask under N.sub.2 atmosphere was charged with Me.sub.3SnCl (28.2 mL, 1.0M in hexane, 28.2 mmol, 1.1 eq.) in 15 mL anhydrous THF and cooled to 0° C. To this was added, by cannula, the Grignard solution over 10 min., and the reaction flask was brought to ambient temperature for an additional 1 hour. The mixture was quenched with chilled, saturated aq. NH.sub.4Cl and Et.sub.2O (60 mL) was added. The organic phase was separated and the aqueous layer was extracted with Et.sub.2O (20 mL×1). The combined organic layers were washed with brine (20 mL×1), dried with anhydrous MgSO.sub.4, filtered, and concentrated to an orange oil. This was pushed through a plug of activated, neutral alumina using hexanes, to provide, after removal of volatiles, the crude stannane reagent as a brown oil, which was purified via vacuum distillation to give pure trimethyl(1 H-inden-2-yl)stannane (4.35 g, 61%) as a yellow oil. .sup.1H-NMR (400 MHz, CDCl.sub.3) δ 7.53 (1H, dd, J=0.8, 7.6 Hz), 7.44 (1H, d, J=7.6 Hz), 7.31 (1H, t, J=7.2 Hz), 7.20 (1H, td, J=7.2, 1.2 Hz), 7.13 (1H, td, J=2.0, 0.8 Hz), 3.53 (2H, d, J=2.0 Hz), 0.32 (9H, s). .sup.13C-NMR (100 MHz, CDCl.sub.3) δ 150.27, 147.06, 145.53, 141.66, 126.28, 124.26, 123.45, 120.22, 45.15, −9.50. ESI-HRMS (mz) calcd for C.sub.12H.sub.20N.sup.120Sn [M+NH.sub.4.sup.+] 298.06177, found 298.06196.

Example 2

Synthesis of Compound 1

[0104] ##STR00006##

[0105] To a stirred solution of trimethyl(1H-inden-2-yl)stannane (7.16 g, 25.7 mmol, 2.2 eq.) in toluene (10 mL) was added a solution of dichlorophenylborane (2 g, 12.6 mmol, 1.0 eq.) in toluene (5 mL) dropwise at room temperature. The resulting yellow solution was then stirred at room temperature for 5 days. The solution was concentrated and the resulting solid was collected by filtration, washed with cold pentane (20 mL), dried in vacuo to give compound 1 (2.92 g, 73%) as a white powder. The filtrate was concentrated and the resulting solid was collected by filtration, washed with cold pentane (6 mL), dried in vacuo to give the second batch of compound 1 (0.3 g, 7%) as a white powder. .sup.11B NMR (128 MHz, C.sub.6D.sub.6) δ 57.8; .sup.1H-NMR (400 MHz, C.sub.6D.sub.6) δ 7.60-7.70 (4H, m), 7.26-7.48 (7H, m), 7.20-7.25 (4H, m), 3.63 (4H, s). .sup.13C-NMR (100 MHz, C.sub.6D.sub.6) δ 153.21, 149.19, 145.45, 134.88, 129.50, 127.67, 127.26, 126.92, 124.37, 123.37, 43.97.

Example 3

Synthesis of Compound 2

[0106] ##STR00007##

[0107] To a stirred solution of compound 1 (1.04 g, 3.27 mmol) in toluene (40 mL) was added LiHMDS (1.2 g, 7.17 mmol, 2.2 eq.) in one portion at room temperature. The resulting yellow solution was then stirred at 80° C. overnight to give a yellow suspension. The suspension was filtered, and the residue was washed with toluene (5 mL) and pentane (10 mL), then dried in vacuo to give compound 2 (1.04 g, 96%) as a yellow powder.

Example 4

Synthesis of Compound 3

[0108] ##STR00008##

[0109] Method A: To the pre-cooled (−35° C.) suspension of compound 2 (0.22 g, 0.67 mmol) in toluene (6 mL) was added ZrCl.sub.4(Me.sub.2S).sub.2 (0.25 g, 7.00 mmol, 1.05 eq.) in one portion. The resulting suspension was then stirred at room temperature for 5 days.

[0110] The mixture was filtered through celite and the residue was washed with toluene (5 mL). The combined filtrates were then discarded. The remaining solids were filtered through using methylene chloride (15 mL), which after concentration provided compound 3 (0.2 g, 56%) as a yellow powder. .sup.11B NMR (128 MHz, CD.sub.2Cl.sub.2) δ-0.9; .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) δ 7.77 (2H, d, J=6.4 Hz), 7.45-7.51 (7H, m), 7.12-7.20 (4H, m), 6.34 (2H, d, J=2 Hz), 5.96 (2H, d, J=2 Hz), 2.18 (6H, s).

##STR00009##

[0111] Method B: To a stirred mixture of compound 4 (0.15 g, 0.27 mmol) in methylene chloride (3 mL) was added dimethyl sulfide (0.25 mL, 3.4 mmol, 12.6 eq.) at room temperature. The resulting yellow mixture was stirred at room temperature for 2 days. The mixture was concentrated in vacuo. Prior to the complete removal of the solvent, excess amount of hexane was added. The powder was collected by filtration and washed with hexane (6 mL×2), dried under high vacuum to give compound 3 (90 mg, 61%) as a yellow powder.

Example 5

Synthesis of Compound 4

[0112] ##STR00010##

[0113] In the same manner (method A) as 3, compound 4 was synthesized as a yellow powder (0.14 g, 42%) from compound 2 (0.2 g, 0.60 mmol) and ZrCl.sub.4(THF).sub.2 (0.23 g, 0.60 mmol, 1.0 eq.) in toluene (6 mL). Crystals suitable for X-ray diffraction were grown by vial-in-vial solvent diffusion of a concentrated solution of 4 in methylene chloride with hexanes. .sup.11B NMR (128 MHz, CD.sub.2Cl.sub.2) δ 9.4; .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) δ 7.91 (2H, dd, J=2.0, 7.6 Hz), 7.46-7.51 (7H, m), 7.11-7.20 (4H, m), 6.28 (2H, d, J=1.6 Hz), 5.81 (2H, d, J=1.6 Hz), 4.58 (4H, s), 2.03 (4H, s).

Example 6

Synthesis of Compound 5

[0114] ##STR00011##

[0115] Method A: To a stirred suspension of compound 2 (0.22g, 0.67 mmol) in benzene (10 mL) was added trimethylphosphine (6 mL, 1.0M in toluene, 6 mmol, 9.0 eq.) at room temperature. The resulting red brown suspension was stirred at room temperature for 30 minutes before ZrCl.sub.4(THF)2 (0.26 g, 0.69 mmol, 1.03 eq.) was added in one portion at room temperature. After the suspension was stirred at room temperature for 5 days, it was filtered through celite and the residue was washed with benzene (6 mL). The combined filtrates were then discarded. The remaining solids were filtered through using methylene chloride (20 mL), which after concentration provided compound 5 (0.17 g, 46%) as a bright yellow powder. .sup.11B NMR (128 MHz, CD.sub.2Cl.sub.2) δ-11.7 (m); .sup.31P NMR (162 MHz, CD.sub.2Cl.sub.2) δ-15.4 (m); .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) δ 7.76-7.78 (2H, m), 7.49 (2H, d, J=8.4 Hz), 7.42 (4H, t, J=8.0 Hz), 7.33-7.37 (1H, m), 7.10-7.17 (4H, m), 6.14 (2H, d, J=2.4 Hz), 6.05 (2H, d, J=2.4 Hz), 1.55 (9H, d, J=10.4 Hz).

##STR00012##

[0116] Method B: To a stirred mixture of compound 4 (0.15 g, 0.27 mmol) in methylene chloride (3 mL) was added a solution of trimethylphosphine (1.5 mL, 1.0 M in toluene, 1.5 mmol, 5.6 eq.) at room temperature. The resulting yellow mixture was stirred at room temperature for overnight. The mixture was concentrated in vacuo. Prior to the complete removal of the solvent, excess amount of hexane was added. The powder was collected by filtration and washed with hexane (6 mL×2), dried under high vacuum to give compound 5 (0.11 g, 71%) as a yellow powder.

Example 7

Synthesis of Compound 6

[0117] ##STR00013##

[0118] To a stirred yellow mixture of compound 4 (0.19 g, 0.35 mmol) in methylene chloride (8 mL) was added pyridine (31 uL, 0.38 mmol, 1.1 eq.) at room temperature. The resulting yellow mixture was stirred at room temperature for overnight. The mixture was concentrated in vacuo, washed with hexane (6 mL×2), dried under high vacuum to give compound 6 (0.18 g, 93.5%) as a bright yellow powder. .sup.11B NMR (128 MHz, CD.sub.2Cl.sub.2) δ 1.4; .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) δ 9.34 (2H, dd, J=1.6, 6.8 Hz), 8.22 (1H, tt, J=1.6, 7.6 Hz), 7.93 (2H, dd, J=1.2, 8.0 Hz), 7.81 (2H, t, J=7.6 Hz), 7.43-7.52 (4H, m), 7.26-7.38 (3H, m), 7.12-7.20 (4H, m), 6.08 (2H, d, J=2.4 Hz), 5.92 (2H, d, J=2.4 Hz).

Example 8

Synthesis of Compound 7

[0119] ##STR00014##

[0120] Preparation of Ph.sub.3PCH.sub.2: To a stirred suspension of Ph.sub.3PCH.sub.3Br (3.57 g, 10 mmol) in diethyl ether (40 mL) was added dropwise a solution of PhLi (5.8 mL, 1.8 M in dibutyl ether, 10.44 mmol, 1.05 eq.) at 0° C. The resulting suspension was stirred at 0° C. for half an hour then at room temperature for 3 hours. The orange solution was concentrated in vacuo and the residual brown foam was stirred in hexane (50 mL) at room temperature for overnight. The mixture was filtered and the filter cake was washed with hexane (8 mL×2), dried under high vacuum to give Ph.sub.3PCH.sub.2 (2.4 g, 87%) as a yellow-green powder. The spectra were consistent with the spectra reported in Crimmin, M. R.; White, A. J. P. Chem. Commun. 2012, 48, 1745-1747.

[0121] To a pre-cooled (−35° C.) suspension of compound 4 (0.18 g, 0.33 mmol) in toluene (9 mL) and benzene (3 mL) was added Ph.sub.3PCH.sub.2 (90 mg, 0.33 mmol, 1.0 eq.) in one portion. The resulting suspension was then stirred at room temperature overnight. The mixture was filtered and the filter cake was washed with hexane (5 mL), dried under high vacuum to provide compound 7 (0.17 g, 69%) as a bright yellow powder. .sup.11B NMR (128 MHz, CD.sub.2Cl.sub.2) δ-11.8; .sup.31P NMR (162 MHz, CD.sub.2Cl.sub.2) δ 28.6, 28.5; .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) δ 7.60-7.85 (3H, m), 7.25-7.56 (21 H, m), 6.96-7.08 (4H, m), 5.76-6.03 (4H, m), 2.84 (2H, t, J=17.2 Hz).

Example 9

Synthesis of Compound 8

[0122] ##STR00015##

[0123] To the pre-cooled (−35° C.) suspension of compound 2 (0.37 g, 1.12 mmol) in toluene (16 mL) was added TiCl.sub.4(THF).sub.2 (0.39 g, 1.17 mmol, 1.05 eq.) in one portion. The resulting suspension was then stirred at room temperature for 5 hours.

[0124] The mixture was filtered through celite and the residue was washed with methylene chloride (6 mL×2). The combined filtrates were then concentrated. The resulting residue was dissolved in methylene chloride, after which time slow addition of hexanes causes precipitation of the desired complex. The solid was collected by filtration, and the precipitation procedure repeated, to give compound 8 (0.2 g, 35%) as a brown powder. .sup.11B NMR (128 MHz, CD.sub.2Cl.sub.2) δ 9.1; .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) δ 7.89 (2H, d, J=6.0 Hz), 7.41-7.50 (7H, m), 7.15-7.24 (4H, m), 6.45 (2H, d, J=1.6 Hz), 5.81 (2H, d, J=1.2 Hz), 4.62 (4H, s), 2.06 (4H, s).

Example 10

Synthesis of Compound 9

[0125] ##STR00016##

[0126] In the same manner as 8, Compound 9 was synthesized as a yellow powder (0.16 g, 27%) from compound 2 (0.4 g, 1.21 mmol) and TiCl.sub.4(Me.sub.2S).sub.2 (0.4 g, 1.27 mmol, 1.05 eq.) in toluene (16 mL). .sup.11B NMR (128 MHz, CD.sub.2Cl.sub.2) δ-1.3; .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) δ 7.76 (2H, d, J=5.6 Hz), 7.43-7.50 (7H, m), 7.18-7.22 (4H, m), 6.48 (2H, s), 5.98 (2H, s), 2.22 (6H, s).

Example 11

Synthesis of Compound 10

[0127] ##STR00017##

[0128] To a stirred suspension of compound 2 (0.3 g, 0.91 mmol) in benzene (10 mL) was added trimethylphosphine (7.3 mL, 1.0M in toluene, 7.3 mmol, 8.0 eq.) at room temperature. The resulting red brown suspension was stirred at room temperature for 30 minutes before TiCl.sub.4(THF).sub.2 (0.32 g, 0.96 mmol, 1.05 eq.) was added in one portion at room temperature. After the suspension was stirred at room temperature for 5 hours, it was filtered through celite and the residue was washed with methylene chloride (6 mL×2). The combined filtrates were then concentrated. The resulting residue was dissolved in methylene chloride, after which time slow addition of hexanes causes precipitation of the desired complex. The solid was collected by filtration, and the precipitation procedure repeated, to give compound 10 (0.2 g, 43%) as a brown powder. .sup.11B NMR (128 MHz, CD.sub.2Cl.sub.2) δ-11.9 (m); .sup.31P NMR (162 MHz, CD.sub.2Cl.sub.2) δ-15.4 (m); .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) δ 7.74 (2H, d, J=5.6 Hz), 7.36-7.44 (7H, m), 7.14-7.21 (4H, m), 6.26 (2H, s), 6.08 (2H, s), 1.58 (9H, d, J=10.8 Hz).

Example 12

Synthesis of Compound 11

[0129] ##STR00018##

[0130] A Schlenk flask was charged with a magnetic stir bar and Mg turnings (264 mg, 11 mmol, 6.7 eq.) and flame-dried under vacuum. After cooling, the flask was purged to N.sub.2, anhydrous THF (3 mL) was added to just cover the turnings, and stirring was commenced. Several drops of 1,2-dibromoethane was added as initiator, and a heat gun used to briefly reflux the contents, after which the flask was placed in a 25° C. water bath. In a separate flame-dried flask under N.sub.2 atmosphere, 2-bromoindene (715 mg, 3.67 mmol, 2.2 eq.) was dissolved in 10 mL anhydrous THF. A cannula was then used to transfer this solution onto the activated magnesium turnings over 5 min, resulting in a red, opaque solution. After 1.5 h, a separate flame-dried flask under N.sub.2 atmosphere was charged with .sup.iPr.sub.2NBCl.sub.2 (0.3 g, 1.65 mmol, 1.0 eq.) in 10 mL anhydrous THF and cooled to −78° C. To this was added, by cannula, the Grignard solution over 10 min., and the reaction flask was brought to ambient temperature for overnight. The pale orange solution was concentrated and the residue was dissolved in CH.sub.2Cl.sub.2 (30 mL). The suspension was filtered through celite and the filtrate was concentrated to provide compound 11 (0.56 g, quant.) as a yellow powder. .sup.11B NMR (128 MHz, CD.sub.2Cl.sub.2) δ 40.4; .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2) 7.37 (2H, d, J=7.6 Hz), 7.33 (2H, d, J=7.6 Hz), 7.19 (2H, t, J=7.6 Hz), 7.06 (2H, td, J=7.6, 1.2 Hz), 6.81 (2H, s), 3.85 (2H, m), 3.38 (4H, s), 1.25 (12H, d, J=6.8 Hz).

Example 13

Synthesis of Compound 12

[0131] ##STR00019##

[0132] In the glovebox, under N.sub.2 atmosphere, a vial was charged with 11 (0.6 g, 1.76 mmol, 1.0 eq.) and 20 mL THF. The mixture was stirred magnetically and cooled to −35° C., after which time solid NaHMDS (0.71 g, 3.87 mmol, 2.2 eq.) was added in one portion. The reaction was allowed to warm slowly to ambient temperature and stirred for a total time of 5 h. The homogenous solution was then cooled back to −35° C. and solid (Me.sub.2N).sub.2ZrCl.sub.2.DME (0.69 g, 1.86 mmol, 1.05 eq.) was added. The reaction mixture was allowed to warm slowly to ambient temperature and stirred overnight. After this time, the THF was removed in vacuo. The residue was filtered through Celite with PhH and concentrated. The resultant residue was dissolved in 20 mL CH.sub.2Cl.sub.2, after which Me.sub.3SiCl (0.67 mL, 5.28 mmol, 3.0 eq.) was added. The reaction mixture was stirred magnetically for overnight. There were some precipitates in the mixture, which was collected by filtration, washed with CH.sub.2Cl.sub.2 (3 mL) and dried in vacuo to give compound 12 (130 mg, 15%) as a yellow powder. The combined filtrates were concentrated and the resulting residue was dissolved in CH.sub.2Cl.sub.2, after which time slow addition of pentanes causes precipitation of 12. The supernatant was decanted, and the procedure repeated, to give the 2.sup.nd batch of 12 (380 mg, 43%) as a yellow powder. .sup.11B NMR (128 MHz, CD.sub.2Cl.sub.2) δ 38.8; .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2) 7.54 (2H, d, J=6.4 Hz), 7.53 (2H, d, J=6.4 Hz), 7.20 (2H, d, J=6.4 Hz), 7.19 (2H, d, J=6.4 Hz), 6.06 (4H, s), 4.00 (2H, m), 1.41 (12H, d, J=6.8 Hz); .sup.13C-NMR (100 MHz, CD.sub.2Cl.sub.2) 131.90, 126.01, 125.15, 104.03, 50.08, 24.60.

Example 14

Synthesis of Compound 13

[0133] ##STR00020##

[0134] In the glovebox, under N.sub.2 atmosphere, a vial was charged with 11 (0.6 g, 1.76 mmol, 1.0 eq.) and 20 mL THF. The mixture was stirred magnetically and cooled to −35° C., after which time solid NaHMDS (0.71 g, 3.87 mmol, 2.2 eq.) was added in one portion. The reaction was allowed to warm slowly to ambient temperature and stirred for a total time of 5 h. The homogenous solution was then cooled back to −35° C. and solid (Me.sub.2N).sub.2TiCl.sub.2 (0.44 g, 1.86 mmol, 1.05 eq.) was added. The reaction mixture was allowed to warm slowly to ambient temperature and stirred overnight. After this time, the THF was removed in vacuo. The residue was filtered through Celite with PhH and concentrated. The residue was taken up in 20 mL CH.sub.2Cl.sub.2, after which trimethylsilylchloride (0.67 mL, 5.28 mmol, 3.0 eq.) was added. The reaction mixture was stirred magnetically for overnight, then the volatiles were removed in vacuo. The residue was dissolved in CH.sub.2Cl.sub.2, and slow addition of excess pentanes causes precipitation of desired complex, which was collected by filtration, washed with pentane and dried in vacuo to give compound 13 (265 mg, 33%) as a brown powder. .sup.11B NMR (128 MHz, CD.sub.2Cl.sub.2) δ 38.7; .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2) δ 7.50 (2H, d, J=6.4 Hz), 7.49 (2H, d, J=6.4 Hz), 7.26 (2H, d, J=6.4 Hz), 7.25 (2H, d, J=6.4 Hz), 6.17 (4H, s), 4.00 (2H, m), 1.42 (12H, d, J=6.8 Hz); .sup.13C-NMR (100 MHz, CD.sub.2Cl.sub.2) δ 136.31, 127.31, 125.79, 111.60, 50.26, 24.66.

Examples 15 to 24

Ethylene Polymerization

[0135] Around 1 mg of a compound 3-13 was suspended in 5 ml toluene. Methylalumoxane (10% in toluene, M:Al=1:1000) was added to the suspended compound in toluene. After around two minutes of shaking, the mixture was transferred under inert atmosphere to a 2 liter autoclave reactor filled with 250 ml of iso-pentane and 100 ml of 1-hexene. The reactor was thermostated at 60° C. An ethylene pressure of 20 bar was applied for 1 hour. After releasing the pressure, the polymer was filtered through an airless filter funnel, washed with diluted hydrochloric acid, water and acetone, and finally dried in vacuum. The polymerization results are presented in Table 1.

TABLE-US-00001 TABLE 1 The ethylene polymerization activities and GPC results of the polyethylenes produced by compounds 3-13. Compound Productivity Mn MW Example Number (g PE/g Cat) (g/mol) (g/mol) MWD 15 3 127500 15098 143218 9.49 16 4 10000 19245 414185 21.52 17 5 163500 2650 10000 3.77 18 6 40000 6549 19405 2.96 19 7 35000 12792 30911 2.42 20 8 500 99431 386172 3.88 21 9 500 51402 328063 6.38 22 10 3750 84753 391080 4.61 23 12 20500 8807 22370 2.54 24 13 2220 16962 73106 4.31

[0136] The GPC results of polyethylenes produced with these catalysts displayed broad and narrow molecular weight distributions. These results can be assigned to the generation of different active sites during activation by methylaluminoxane (MAO). The GPC spectra of polyethylenes produced by compounds 3 and 4 are shown (see FIG. 1).