Metal complex with a cyclic amidine ligand

Abstract

The present invention relates to a A metal complex of formula 1
C.sub.yYML.sub.jX.sub.n(formula 1) wherein Cy is a cyclopentadienyl-type ligand; M is a metal of group 4; L is a neutral Lewis basic ligand wherein the number of said neutral ligands j is in the range of 0 to the amount that satisfies the 18-electron rule: X is an anionic ligand; n is an integer denoting the number of anionic ligands X and is 1 or 2, preferably is 2; Y is a cyclic amidine-containing ligand moiety represented by formula 2 ##STR00001## wherein the amidine-containing ligand is covalently bonded to the metal M via the imine nitrogen atom N.sup.2; S is a CH.sub.2 unit, and t is the integer number denoting the number of S and is in the range of 1-4, more preferably in the range of 1-2, most preferably is 1; Sub.sub.1 is an aliphatic cyclic or linear substituent comprising a group 14 atom through which Sub.sub.2 is bonded to the amine nitrogen atom N.sup.1; Sub2 is an optionally substituted C2 unit in which the 2 carbon atoms may be sp.sup.2 or sp.sup.3 hybridized.

Claims

1. A metal complex of formula 1
CyYML.sub.jX.sub.n(formula 1) wherein Cy is a cyclopentadenyl-type ligand; M is a metal of group 4; L is a neutral Lewis basic ligand wherein the number of said neutral ligands j is 0 to an amount that satisfies the 18-electron rule; X is an anionic ligand; n is an integer denoting the number of anionic ligands X and is 1 or 2; Y is a cyclic amidine-containing ligand moiety represented by formula 2 ##STR00050## wherein the amidine-containing ligand is covalently bonded to the metal M via the imine nitrogen atom N.sup.2; S is a CH.sub.2 unit, and t is the integer number denoting the number of S and is 1-4; Sub.sub.1 is an aliphatic cyclic or linear substituent comprising a group 14 atom through which Sub is bonded to the amine nitrogen atom N.sup.1; and Sub2 is an optionally substituted C2 unit in which the 2 carbon atoms may be sp.sup.2 or sp.sup.3 hybridized.

2. The metal complex according to claim 1, wherein L is an ether, a thioether, an amine, a tertiary phosphane, an imine, a nitrile, an Isonitrile, a bidentate donor, or an oligodentate donor.

3. The metal complex according to claim 1, wherein j is 0, 1 or 2.

4. The metal complex according to claim 1, wherein M is titanium.

5. The metal complex according to claim 1, wherein X is a halogen atom, a C1-10 alkyl group, a C7-20 aralkyl group, a C6-20 aryl group or a C1-20 hydrocarbon-substituted amino group.

6. The metal complex according to claim 1, wherein Sub1 is an alkyl, alkenyl or alkynyl residue with 1 to 20 carbon atoms, unsubstituted or substituted with halogen, amido, silyl or aryl radicals.

7. The metal complex according to claim 1, wherein Y has the general formula 2a ##STR00051## wherein R.sub.1-R.sub.4 are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted C1-10 alkyl group, an optionally substituted C1-10 alkoxy group, or the general formula 2b ##STR00052## wherein R.sub.5-R.sub.6 are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted C1-10 alkyl group, an optionally substituted C1-10 alkoxy group, or the adjacent R.sub.5-R.sub.6 may be linked to form an aromatic ring optionally substituted.

8. The metal complex of claim 1, wherein Cy is selected from the group consisting of unsubstituted or substituted cyclopentadienyl groups, substituted or unsubstituted indenyl groups, substituted or unsubstituted fluorenyl groups, substituted or unsubstituted tetrahydroindenyl groups, substituted or unsubstituted tetrahydrofluorenyl groups, substituted or unsubstituted octahydrofluorenyl groups, substituted or unsubstituted benzoindenyl groups, substituted or unsubstituted heterocyclopentadienyl groups, substituted or unsubstituted heteroindenyl groups, substituted or unsubstituted heterofluorenyl groups, or their isomers.

9. The metal complex of claim 1, wherein: Cy is 1,2,3,4,5-pentamethyl-cyclopentadienyl; M is titanium; L is an ether, a thioether, an amine, a tertiary phosphane, an imine, a nitrile, an isonitrile, a bidentate donor, or an oligodentate donor; j is 0, 1 or 2; X is a halogen atom, a C1-10 alkyl group, a C7-20 aralkyl group, a C6-20 aryl group or a C1-20 hydrocarbon-substituted amino group; n is 2; and Y is a ligand moiety of the general formula 2a ##STR00053## wherein R.sub.1-R.sub.4 are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted C1-10 alkyl group, an optionally substituted C1-10 alkoxy group, or a ligand moiety of the general formula 2b ##STR00054## wherein R.sub.5-R.sub.6 are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted C1-10 alkyl group, an optionally substituted C1-10 alkoxy group, or the adjacent R.sub.5-R.sub.8 may be linked to form an aromatic ring optionally substituted, wherein: Sub1 is an alkyl, alkenyl or alkynyl residue with 1 to 20 carbon atoms, unsubstituted or substituted with halogen, amido, silyl or aryl radicals, S is a CH.sub.2 unit, and t is 1.

10. A process for manufacturing the metal complex according to claim 1, wherein a metal complex of the formula 3
CyML.sub.jX.sub.n(formula 3) is reacted with YH or YH.HHal, the hydrohalogen acid salt of YH wherein Hal is halogen.

11. A catalyst system comprising a) a metal complex of the formula 1 according to claim 1, and b) a scavenger.

12. The catalyst system according to claim 11, wherein the scavenger b) is a hydrocarbyl of a metal or metalloid of group 1-13 or its reaction products with at least one sterically hindered compound containing a group 15 or 16 atom.

13. A process for the preparation of a polymer by polymerizing at least one olefinic monomer, the process comprising contacting at least one olefinic monomer with the metal complex according to claim 1.

14. The process according to claim 13, wherein: the metal complex is in the form of a catalyst system comprising the metal complex and a scavenger; and the at least one olefinic monomer comprises ethylene and at least one C.sub.3-C.sub.12--olefin.

15. The process according to claim 14, wherein the at least one olefinic monomer comprises ethylene, at least one C.sub.3-12 alpha olefin and at least one non-conjugated diene.

16. The process according to claim 15, wherein the at least one non-conjugated diene is selected from the group consisting of 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-vinylnorbornene, 2,5-norbornadiene, dicyctopentadiene and vinylcyclohexene.

Description

(1) Below, the invention will be elucidated on the basis of the following examples and comparative experiments, without being limited thereto.

(2) Test Methods.

(3) Size Exclusion Chromatography (SEC) Coupled to Refractive Index (RI) and Differential Viscometry (DV) Detection Equipment: PL220 (Polymer Laboratories) SEC with PL220 DRI concentration detector and Viscotek 220R viscometry detector. Detectors are operated in parallel configuration. Degasser: PL-DG 802 Data processing: Viscotek data processing software, TriSEC 2.7 or higher version Columns: PLgel Olexis (4) Calibration: Universal calibration with linear polyethylene (PE) standard (molecular weight 0.4-4000 kg/mol) Temperature: 160 C. Flow: 1.0 ml/min Injection volume: 0.300 ml Solvent/eluent: Distilled 1,2,4-trichlorobenzene with about 1 g/l of Ionol stabilizer Sample preparation: Dissolving for 4 hours at approx. 150 C. Filtration through 1.2 micron Ag filter Sample concentration approx. 1.0 mg/ml

(4) Intrinsic Viscosity (IV) was measured at 135 C. in decahydronaphthalene as solvent,

(5) Fourier transformation infrared spectroscopy (FT-IR), was used to determine the composition of the copolymers according to the method that is known in the art. The FT-IR measurement gives the composition of the various monomers in weight per cents relative to the total composition.

(6) NMR (.sup.1H, 300 MHz, .sup.13C 75.7 MHz, and .sup.19F at 282 MHz) spectra were measures on a Bruker Avance 300 spectrometer.

(7) Part I: Synthesis of Ligands and Compounds:

(8) General.

(9) All experiments were carried out under nitrogen using Schlenk line techniques. Toluene, hexane and dichloromethane were provided by solvent purification system Braun SPS-800. All other reagents were used as received without further purification.

Synthesis of Compounds for the Comparative Experiments

Synthesis of Me5CpTiCl2(NC(Ph)(iPr2N)) (Compound A)

(10) Me.sub.5CpTiCl.sub.2(NC(Ph)(iPr.sub.2N)) was prepared as described for compound 6 in WO 2005/090418.

(11) ##STR00006##

Synthesis of Me5CpTiCl2(NC(Ph)(iPr2N)) (Compound AM)

(12) To a stirring toluene (15 mL) solution of Cp*Ti(NC(Ph)N.sup.iPr.sub.2)Cl.sub.2 (3) (1.00 g, 2.20 mmol) was added dropwise MeLi (2.80 ml, 1.6 M in Et.sub.2O, 4.0 mmol) and the resulting solution was stirred for 16 h. The volatiles were then removed in vacuo and the yellow solid was then extracted into n-hexanes (50 ml), Concentration of the solution to ca, 15 ml and subsequent storage at 30 C. for 24 h resulted in crystallisation of the desired product as large yellow crystals which were isolated and dried in vacuo. Yield=0.37 g (40%). The product was characterized by .sup.1H-NMR and .sup.13C-NMR.

(13) ##STR00007##

Synthesis of Me5CpTiCl2(NC(Ph)(2,6-Me2PhN) (Compound B)

(14) Me.sub.5CpTiCl.sub.2(NC(Ph)(2,6-Me.sub.2PhN) was prepared as described for compound 11 in WO 2005/090418.

(15) ##STR00008##

Synthesis of Me5CpTiCl2(NC(Ph)(2,6-Me2PhN) (Compound BM)

(16) To a solution of Compound B (2.02 g, 4.14 mmol) in toluene (150 ml) was added methyl magnesium chloride solution (3M in THF, 3.08 mL, 9.24 mmol) dropwise at 80 C., Mixture was allowed to warm to room temperature and stirred overnight. The mixture was concentrated and hexane was added (50 ml). It was filtered off and mixture was concentrated to approx. 20 ml. Solution was stored at 80 C. After 24 h remaining liquid was removed by decantation and resulting solid was dried under reduced pressure to yield the product as a yellow powder (0.833 g, 1.86 mmol, 45%),

(17) The powder was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 8.08-6.79 (m, 7H); 4.12 (s, 2H); 2.18 (s, 6H); 1.89 (s, 15H); 0.48 (s, 6H) and .sup.13C NMR (75 MHz) (C.sub.6D.sub.6) (ppm):141.9; 138.4; 138.0; 136.7; 130.8; 128.8; 128.8; 128.2; 124.6; 123.3; 120.6; 52.5; 47.3; 18.8; 12.4.

(18) ##STR00009##

Synthesis of Me5CpTiCl2(NC(Ph)(2,4,6-Me3PhN) (Compound C)

(19) A mixture of 2-(2,4,6-trimethylphenyl)isoindolin-1-imine hydrobromide (2.00 g, 6.04 mmol) and pentamethylcyclopentadienyl titanium trichloride (1.748 g, 6.04 mmol) was dissolved in toluene (60 ml) and triethylamine (2.10 mL, 15.1 mmol) was added. If was stirred at 50 C. overnight. If was filtered off and the filtrate was concentrated to approx. 5 ml. Hexane (30 ml) was added and stirred for 20 min. It was filtered off and dried under reduced pressure to yield the product as a yellow solid (1.84 g, 3.68 mmol, 61%).

(20) The powder was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 2.00 (s, 15H); 2.08 (s, 3H); 2.12 (s, 6H); 3.97 (s, 2H); 8.79 (s, 2H); 6.86 (d, 1H); 7.10 (m, 2H); 8.26 (d, 1H) and .sup.13C NMR (75 MHz) (C.sub.6D.sub.6) (ppm): 141.2; 137.2; 131.6; 129.7; 129.1; 127.8; 126.1; 123.0; 54.0; 21.4; 18.9; 13.4.

(21) ##STR00010##

Synthesis of Me5CpTiMe2(NC(Ph)(2,4,6-Me3PhN) (Compound CM)

(22) To a solution of Compound C (503 mg, 1.00 mmol) in toluene (40 ml) was added methyl magnesium chloride solution (3M in THF, 1.00 mL, 3.00 mmol) dropwise at 80 C. Mixture was allowed to warm to room temperature and stirred overnight. Trimethylsilyl chloride (0.150 mL, 1.15 mmol) was added and stirred for 15 min. Volatiles ware removed under reduced pressure and hexane was added (50 mL). It was filtered off and volatiles were removed under reduced pressure to yield the product as a yellow powder (230 mg, 0.497 mmol, 50%).

(23) The powder was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm); 0.50 (s, 6H); 1.90 (s, 15H); 2.09 (s, 3H); 2.18 (s, 6H); 4.16 (s, 2H); 6.79 (s, 2H); 8.97 (d, 1H); 7.18 (m, 2H); 7.95 (d, 1H) and .sup.13C NMR (75 MHz) (C.sub.6D.sub.6) (ppm): 141.8; 137.9; 137.5; 130.8; 129.5; 124.6; 123.3; 120.5; 52.8; 47.2; 21.4; 18.8; 12.4.

(24) ##STR00011##

Synthesis of Compounds for Inventive Examples

Synthesis of the 2-cyclopentylisoindolin-1-imine hydrobromide (Ligand 1)

(25) 2-(Bromomethyl)benzonitrile (1.9 g, 10.0 mmol) was dissolved in toluene (20 mL) and cyclopentylamine (0.851 g, 10.0 mmol), dissolved in toluene (10 mL), was added dropwise within 20 min. It was stirred at 50 overnight. The solvent was evaporated to approx. 5 ml and diethylether (40 mL) was added. It was filtered off, washed with diethylether (320 ml) and dried under reduced pressure to yield the product as a white solid (1.49 g, 5.30 mmol, 53%).

(26) The powder was characterized by .sup.1H NMR (300 MHz) (CDCl.sub.3) (ppm): 1.58-1.73 (m, 2H); 1.79-1.96 (m, 4H); 2.31-2.44 (m, 2H); 4.69 (s, 2H); 5.21 (m, 1H); 7.53 (d, 1H); 7.63 (m, 2H); 8.93 (d, 1H); 9.65 (s, 1H); 10.18 (s, 1H).

(27) ##STR00012##

Synthesis of Me5CpTiCl2(NC(Ph)(c-C5H9N) (Compound 1)

(28) A mixture of 2-cyclopentylisoindolin-1-imine hydrobromide (0.500 g, 1.78 mmol) and pentamethylcyclopentadienyl titanium trichloride (0.515 g, 1.78 mmol) was dissolved in toluene (50 ml) and triethylamine (1.30 mL, 9.38 mmol) was added, it was stirred at 50 C. overnight. Toluene (40 ml) was added and the hot solution (70 C.) was filtered off. The filtrate was concentrated to approx. 20 ml and hexane (50 mL) was added and stirred for 20 min. It was filtered off and dried under reduced pressure to yield the product as a yellow solid (0.405 g, 0.836 mmol, 50%).

(29) The powder was characterised by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 1.29-1.69 (8H, m); 2.20 (s, 15H); 3.54 (2H, s); 4.28-4.42 (1H, m); 6.81-6.88 (1H, m); 7.05-7.11 (2H, m); 7.90-7.98 (1H, m).

(30) ##STR00013##

Synthesis of Me5CpTiMe2(NC(Ph)(c-C5H9N) (Compound 1M)

(31) To a solution of Compound 1 (200 mg, 0.440 mmol) in toluene (30 mL) was added methyl magnesium chloride solution (1M in THF, 1.76 mL, 1.78 mmol) dropwise at 80 C. Mixture was allowed to warm to room temperature and stirred overnight. Trimethylsilyl chloride (0.10 ml) was added and stirred for 30 min. The mixture was concentrated and hexane was added (100 ml), it was filtered off and solvent was evaporated to dryness to yield Compound 1M as a yellow solid (60 mg, 31% Yield).

(32) The powder was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 0.68 (s, 6H); 1.19-1.37 (m, 4H); 1.57 (m, 2H); 1.81 (m, 2H); 2.07 (s, 15H); 3.71 (s, 2H); 4.85 (m, 1H); 6.95 (d, 1H); 7.13 (m, 2H); 7.82 (d, 1H).

(33) ##STR00014##

Synthesis of the 2-cyclohexylisoindolin-1-imine hydrobromide (Ligand 2)

(34) 2-(Bromomethyl)benzonitrile (4.90 g, 25.0 mmol) was dissolved in toluene (10 mL) and cyclohexylamine (2.48 g, 25.0 mmol), dissolved in toluene (10 ml), was added dropwise within 20 min. If was stirred at 50 C. overnight. The solvent was evaporated to approx. 10 ml and diethylether (20 ml) was added. It was filtered off, washed with diethylether (220 ml) and dried under reduced pressure to yield the product as a white solid (6.71 g, 22.8 mmol, 91%).

(35) The powder was characterized by .sup.1H NMR (300 MHz) (CDCl.sub.3) (ppm): 1.10-2.14 (10H, m); 4.67 (2H, s); 4.95 (1H, m); 7.51 (1H, d); 7.58-7.68 (2H, m); 9.05 (1H, d); 9.81 (1H, s); 10.25 (1H, s).

(36) ##STR00015##

Synthesis of Me5CpTiCl2(NC(Ph)(c-C5H11N) (Compound 2)

(37) A mixture of 2-cyclohexylisoindolin-1-imine hydrobromide (2.95 g, 10.0 mmol) and pentamethylcyclopentadienyl titanium trichloride (2.89 g, 10.0 mmol) was dissolved in toluene (50 mL) and triethylamine (3.49 ml, 25.0 mmol) was added. It was stirred at 50 C. overnight. Toluene (40 ml) was added and the hot solution (70 C.) was filtered off. The filtrate was concentrated to approx. 20 mL and hexane (50 mL) was added and stirred for 20 min. It was filtered off and dried dried under reduced pressure to yield the product as a yellow solid (1.53 g, 3.27 mmol, 33%).

(38) The powder was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 0.85-1.70 (10H, m); 2.18 (s, 15H); 3.55 (2H, s); 4.15 (1H, m); 6.85 (1H, m); 7.07 (2H, m); 7.90 (1H, m) and .sup.13C NMR (75 MHz) (C.sub.6D.sub.6) (ppm): 141.3; 131.2; 127.1; 124.9; 123.0; 53.5; 48.2; 32.0; 26.3; 26.1; 13.6.

(39) ##STR00016##

Synthesis of Me5CpTiMe2(NC(Ph)(c-C5H11N) (Compound 2M)

(40) To a solution of Compound 2 (500 mg, 1.07 mmol) in toluene (40 mL) was added methyl magnesium chloride solution (3M in THF, 1.07 mL, 3.21 mmol) dropwise at 80 C. Mixture was allowed to warm to room temperature and stirred overnight. Trimethylsilyl chloride (0.15 ml) was added and stirred for 30 min. The mixture was concentrated and hexane was added (100 mL). It was filtered oft and solvent was evaporated to dryness to yield Compound 2M as a yellow solid (0.35 g, 76% Yield).

(41) The powder was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 0.66 (s, 6H); 1.07-1.80 (m, 10H); 2.07 (s, 15H); 3.76 (s, 2H); 4.32 (m, 1H); 6.96 (d, 1H); 7.15 (m, 2H); 7.83 (d, 1H) and .sup.13C NMR 75 MHz (C.sub.6D.sub.6) (ppm): 141.8; 130.4; 124.1; 123.1; 120.2; 52.1; 47.5; 45.3; 31.9; 26.7; 26.4; 12.6.

(42) ##STR00017##

Synthesis of the 2-cycloheptylisoindolin-1-amine hydrobromide (Ligand 3)

(43) 2-(Bromomethyl)benzonitrile (1.96 g, 10.0 mmol) was dissolved in toluene (50 mL) and cycloheptylamine (1.13 g, 10.0 mmol) was added dropwise within 20 min. It was stirred at 50 C. for 5 h. The solvent was removed by decantation, the white solid residue was washed with diethylether (315 mL) and dried under reduced pressure overnight to yield the product as a white powder (1.56 g. 5.05 mmol, 51%)

(44) The powder was characterized by .sup.1H NMR (300 MHz) (CDCl.sub.3) (ppm): 1.51-1.98 (m, 10H); 2.15 (m, 2H); 4.89 (s, 2H); 5.09 (m, 1H); 7.52 (d, 1H); 7.63 (m, 2H); 8.98 (d, 1H); 9.77 (s, 1H); 10.28 (s, 1H).

(45) ##STR00018##

Synthesis of Me5CpTiCl2(NC(Ph)(c-C7H13N) (Compound 3)

(46) A mixture of 2-cycloheptylisoindolin-1-imine hydrobromide (500 mg, 1.62 mmol) and pentamethylcyclopentadienyl titanium trichloride (468 mg, 1.62 mmol) was dissolved in toluene (40 mL) and triethylamine (0.80 mL, 4.33 mmol) was added. It was stirred at 50 C. for 4 h and another portion of triethylamine (0.80 mL, 4.33 mmol) was added. It was stirred at 50 C. for 72 h. The solution was filtered off, the filtrate was concentrated to approx. 5 mL and hexane (40 mL) was added and stirred for 20 min. It was filtered off and dried dried under reduced pressure to yield the product as a yellow solid (303 mg, 0.630 mmol, 39%).

(47) The powder was characterized by .sup.1H HUB (300 MHz) (C.sub.6D.sub.6) (ppm): 1.09-1.68 (m, 12H); 2.19 (s, 15H); 3.55 (s, 2H); 4.28-4.42 (m, 1H); 6.81-6.89 (m, 1H); 7.05-7.11 (m, 2H); 7.10-7.17 (m, 1H).

(48) ##STR00019##

Synthesis of Me5CpTiMe2(NC(Ph)(c-C7H13N) (Compound 3M)

(49) To a solution of Compound 3 (200 mg, 0.42 mmol) in toluene (30 ml) was added methyl magnesium chloride solution (1M in THF, 1.66 ml, 1.66 mmol) dropwise at 80 C. Mixture was allowed to warm to room temperature and stirred overnight. Trimethylsilyl chloride (0.10 ml) was added and stirred for 30 mm. The mixture was concentrated and hexane was added (100 ml). It was filtered off and solvent was evaporated to dryness to yield Compound 3M as a yellow solid (110 mg, 0.247 mmol, 59%).

(50) The powder was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 0.87 (s, 8H); 1.23-1.61 (m, 12H); 2.09 (s, 15H); 3.78 (s, 2H); 4.53 (m, 1H); 6.98 (m, 1H); 7.14 (m, 2H); 7.82 (m, 1H),

(51) ##STR00020##

Synthesis of the 2-cyclooctylisoindolin-1-imine hydrobromide (Ligand 4)

(52) 2-(Bromomethyl)benzonitrile (3.00 g, 15.3 mmol) and cyclooctylamine (1.95 g, 15.3 mmol) were mixed without solvent at room temperature. The reaction was performed at room temperature for 5 min. The resulting dark gel was washed with diethylether (320 ml) to yield the product as a white solid (3.72 g, 11.5 mmol, 75%).

(53) The powder was characterized by .sup.1H NMR (300 MHz) (CDCl.sub.3) (ppm): 1.7 (m, 15H); 4.7 (s, 2H); 5 (s, 1H); 7.6 (m, 4H) and .sup.13C NMR (75 MHz) (CDCl.sub.3) (ppm): 24.2; 27.4; 31.3; 52.3; 56.9; 126.7; 129.4; 160.8.

(54) ##STR00021##

Synthesis of Me5CpTiCl2(NC(Ph)(c-C8H15N) (Compound 4)

(55) To a solution of pentamethylcyclopentadienyl titanium trichloride (1.50 g, 5.30 mmol) and 2-cyclooctylisoindolin-1-imine hydrobromide (1.70 g, 5.30 mmol) in toluene (30 mL) was added triethylamine (2.80 mL, 21.0 mmol). The reaction was heated up to 50 C. and stirred overnight. The solution was filtered off, the filtrate was concentrated to approx. 10 mL. The flask was stored at 20 C. After 2 days remaining liquid was removed by decantation and resulting solid was dried under reduced pressure to yield the product as a bright-yellow powder (2.12 g, 4.24 mmol, 81%).

(56) The powder was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 1.26-1.89 (m, 14H); 2.30 (s, 15H); 3.68 (s, 2H); 4.53 (s, 1H); 7.02 (m, 1H); 7.20 (m, 2H); 8.07 (m, 1H) and .sup.13C NMR (75 MHz) (C.sub.6D.sub.6) (ppm): 13.6; 25.4; 26.4; 27.1; 32.6; 48.1; 54.1; 123.0; 125.2; 127.1; 131.2; 135.2; 141.3; 159.9.

(57) ##STR00022##

Synthesis of Me5CpTiMe2(NC(Ph)(c-C8H15N) (Compound 4M)

(58) To a solution of Compound 4 (400 mg, 0.800 mmol) in toluene (30 ml) was added methyl magnesium chloride solution (3M in Et.sub.2O, 0.533 ml, 1.60 mmol) dropwise at 80 C. Mixture was allowed to warm to room temperature and stirred overnight. Hexane was added (15 ml), the resulting suspension was filtered off and solvent was evaporated to dryness to yield Compound 4M as a yellow solid (0.29 g, 0.63 mmol, 78%).

(59) The powder was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 0.78 (s, 8H); 1.32-1.89 (m, 14H); 2.20 (s, 15H); 3.89 (s, 2H); 4.76 (s, 1H); 7.02 (m, 1H); 7.20 (m, 2H); 8.07 (m, 1H) and NMR (75 MHz) (C.sub.6D.sub.6) (ppm): 12.7; 25.6; 26.5; 27.3; 32.6; 45.6; 47.4; 52.6; 123.0; 125.2; 127.1; 131.2; 135.2; 141.3; 159.9.

(60) ##STR00023##

Synthesis of the 2-cyclododecylisoindolin-1-imine hydrobromide (Ligand 5)

(61) 2-(Bromomethyl)benzonitrile (3.00 g, 15.3 mmol) and cyclododecylamine (2.80 g, 15.3 mmol) were mixed without solvent at room temperature. The reaction was performed at room temperature for 5 min. The resulting dark gel was washed with diethylether (320 ml) to yield the product as a white solid (4.40 g, 11.6 mmol, 78%). The powder was characterized by .sup.1H NMR (300 MHz) (CDCl.sub.3) (ppm); 1.38 (m, 22H); 4.75 (s, 2H); 4.98 (s, 1H); 7.80 (m, 3H), 9.02 (d, 1H).

(62) ##STR00024##

Synthesis of Me5CpTiCl2(NC(Ph)(c-C2H23N) (Compound 5)

(63) To a solution of pentamethylcyclopentadienyl titanium trichloride (1.53 g, 5.27 mmol) and 2-cyclododecylisoindolin-1-imine hydrobromide (2.00 g, 5.27 mmol) in toluene (30 ml) was added triethylamine (2.80 ml, 21.0 mmol). The reaction was heated up to 50 C. and stirred overnight. The solution was filtered off, the filtrate was concentrated to approx. 10 mL. The flask was stored at 80 C. After 2 days remaining liquid was removed by decantation and resulting solid was dried under reduced pressure to yield the product as a yellow powder (2.20 g, 3.95 mmol, 75%).

(64) The powder was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 1.22-1.78 (m, 22H); 2.31 (s, 15H); 3.76 (s, 2H); 4.5 (m, 1H, (CH.sub.2).sub.2CHN); 6.98-7.33 (m, 4H) and .sup.13C NMR (75 MHz) (C.sub.6D.sub.6) (ppm): 13.7; 22.9; 24.2; 24.5; 24.9; 25.2; 29.1; 49.1; 52.3; 122.9; 125.9; 126.0; 127.2; 129.7; 131.2; 141.1; 161.4.

(65) ##STR00025##

Synthesis of Me5CpTiMe2(NC(Ph)(c-C2H23N)(Compound 5M)

(66) To a solution of Compound 5 (400 mg, 0,719 mmol) in toluene (30 mL) was added methyl magnesium chloride solution (3.sub.M in Et.sub.2O, 0.473 mL, 1.42 mmol) dropwise at 80 C. Mixture was allowed to warm to room temperature and stirred overnight. A color change from red to orange was observed. Hexane was added (15 ml), the resulting suspension was filtered off and solvent was evaporated to dryness to yield Compound 5M as a yellow solid (0.29 g, 0.56 mmol, 81%).

(67) The powder was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 0.78 (s, 6H); 1.48-1.70 (m, 22H); 2.19 (s, 15H); 3.95 (s, 2H); 4.81 (m, 1H); 7.12 (m, 1H); 7.27 (m, 2H); 7.86 (m, 1H) and .sup.13C NMR (75 MHz) (C.sub.6D.sub.6) (ppm): 11.0; 21.5; 22.6; 22.7; 23.1; 23.1; 27.5; 44.7; 46.1; 48.0; 118.5; 121.3; 122.7; 126.5; 128.7; 135.4; 139.7; 156.0.

(68) ##STR00026##

Synthesis of the 2-tert-butyl-1-imine hydrobromide (Ligand 6)

(69) 2-(Bromomethyl)benzonitrile (4.97 g, 25.4 mmol) was dissolved in toluene (100 mL) and tert-butylamine (2.69 g, 25.4 mmol was added at ambient temperature. It was heated to reflux (bath temperature 115 C.) and stirred for 30 h. Another portion of tert-butylamine (1.62 ml, 15.3 mmol) was added and stirred at reflux for another 30 h. If was filtered off, washed toluene (50 mL) and dried under reduced pressure to yield the product as a light pink solid (5.06 g, 18.8 mmol, 75%).

(70) The powder was characterized by .sup.1H NMR (300 MHz) (CDCl.sub.3) (ppm): 9.07 (d, 1H), 7.91-7.10 (m, 4H), 4.96 (s, 2H), 1.77 (s, 9H) and .sup.13C NMR (75 MHz) (CDCl.sub.3) (ppm): 161.0; 140.1; 133.7; 130.4; 129.5; 126.3; 122.5; 58.1; 55.8; 28.53.

(71) ##STR00027##

Synthesis of Me5CpTiCl2(NC(Ph)(c-C4H9N) (Compound 6)

(72) To a solution of pentamethylcyclopentadienyl titanium trichloride (0.891 g, 3.08 mmol) and 2-tert-butyl-1-imine hydrobromide (0.824 g, 3.07 mmol) in toluene (100 ml) was added triethylamine (1.02 ml, 7.36 mmol). The reaction was heated up to 50 C. and for 94 h. The solution was filtered off, the filtrate was concentrated to approx. 10 mL. The flask was stored at 80 C. After 2 days remaining liquid was removed by decantation and resulting solid was dried under reduced pressure to yield the product as a yellow powder (300 mg, 0.672, 22%).

(73) The powder was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 8.09-6.71 (m, 4H); 3.63 (s, 2H); 2.19 (s, 15H); 1.28 (s, 9H) and .sup.13C NMR (75 MHz) (C.sub.6D.sub.6) (ppm): 140.2; 137.1; 131.1; 127.3; 125.4; 122.5; 56.7; 51.4; 28.7; 13.6.

(74) ##STR00028##

Synthesis of Me5CpTiMe2(NC(Ph)(c-C4H9N) (Compound 6M)

(75) To a solution of Compound 6 (1.00 g, 2.30 mmol) in toluene (40 ml) was added methyl lithium solution (1.6 M in hexanes, 3.10 ml, 5.00 mmol) dropwise at 80 C. A color change to red-orange was observed immediately. Mixture was allowed to warm to room temperature and stirred for 4 h. Trimethylsilyl chloride (0.150 ml, 1.15 mmol) was added and stirred for 15 min. Volatiles were removed under reduced pressure. I was extracted with hexane (315 mL), filtered and removal of solvent under reduced pressure to yield the product as a waxy solid (0.58 g, 1.43 mmol, 64%).

(76) The waxy solid was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 7.61 (m, 1H); 7.19-7.13 (m, 2H); 6.91 (m, 1H); 3.85 (s, 2H); 2.07 (s, 15H); 1.44 (s, 9H), 0.64 (s, 8H) and .sup.13C NMR (75 MHz) (C.sub.6D.sub.6) (ppm); 158.3; 140.1; 138.1; 130.0; 127.6; 123.6; 122.3; 119.9; 55.2; 50.0; 47.2; 28.1; 12.3.

(77) ##STR00029##

Synthesis of the 2-adamantylisoindolin-1-imine hydrobromide (Ligand 7)

(78) 2-(Bromomethyl)benzonitrile (2.60 g, 13.3 mmol) was dissolved in toluene (150 ml) and adamantylamine (2.00 g, 13.3 mmol) was added. It was heated to reflux (bath temperature 115 C.) and stirred overnight. It was filtered off to yield the product as a white solid (3.79 g, 10.9 mmol, 82%).

(79) The powder was characterized by .sup.1H NMR (300 MHz) (CDCl.sub.3) (ppm): 1.7 (m, 6H); 2.0 (m, 3H); 2.3 (m, 6H); 5.0 (s, 2H); 7.6 (m, 4H); 8.5 (s, 1H) and .sup.13C NMR (75 MHz) (CDCl.sub.3) (ppm): 29.9; 35.77; 39.6; 59.9; 130.4; 140.3; 169.6.

(80) ##STR00030##

Synthesis of Me5CpTiCl2(NC(Ph)(AdamantylN) (Compound 7)

(81) To a solution of pentamethylcyclopentadienyl titanium trichloride (1.50 g, 5.20 mmol) and 2-adamantylisoindolin-1-imine hydrobromide (1.80 g, 5.20 mmol) in toluene (30 mL) was added triethylamine (2.80 ml, 21.0 mmol). The reaction was heated up to 50 C. and stirred for 7 d. The solution was filtered off, the filtrate was concentrated to approx. 10 mL. The flask was stored at 80 C. After 3 days remaining liquid was removed by decantation and resulting solid was dried under reduced pressure to yield the product as a yellow powder (191 mg, 0.364 mmol, 7%).

(82) The powder was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm); 1.70 (m, 6H); 1.85 (m, 3H); 2.1 (m, 8H); 2.29 (m, 15H); 3.82 (s, 2H); 7.11-7.33 (m, 4H) and .sup.13C NMR (75 MHz) (C.sub.6D.sub.6) (ppm): 13.5; 30.5; 36.6; 40.5; 50.4; 58.1; 122.4; 125.5; 127.1; 131.1.

(83) ##STR00031##

Synthesis of the 2-octadecylisoindolin-1-imine (Ligand 8)

(84) 2-Bromomethylbenzonitrile (7.65 g, 39.0 mmol) was dissolved in toluene (50 mL) and octadecylamine (8.09 g, 30 mmol), dissolved in 150 ml of toluene (very bad solubility), is added drop-wise within 1 hour. The mixture was stirred at 70 C. for 3 d. The mixture was concentrated to approx. 50 mL and diethylether (70 ml) was added. It was filtered off and washed with diethylether (225 ml). The solid was dried under reduced pressure for 4 hours to yield the hydrobromide salt of Ligand 8 (13.9 g, 38.8 mmol, 99%).

(85) The hydrobromide salt of Ligand 8 was neutralized due to poor solubility in toluene and therefore low reactivity in the next step. Neutralization was performed according to the following procedure:

(86) Hydrobromide salt of Ligand 8 (5.00 g, 10.7 mmol) was added to an aqueous solution of sodium hydroxide (4.30 g NaOH in 100 ml H.sub.2O). The mixture was stirred for 10 minutes, it was extracted with diethylether (350 ml), the combined organic phase was dried over MgSO.sub.4, filtered and the solvent removed under reduced pressure to yield the product as a light yellow solid (3.26 g, 8.48 mmol, 79%).

(87) Ligand 8 was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 0.87 (t, 3H); 1.25 (m, 30H); 1.70 (m, 2H); 3.61 (t, 2H); 4.44 (s, 2H); 7.37-7.50 (m, 3H); 7.83 (d, 1H).

(88) ##STR00032##

Synthesis of Me5CpTiCl2(NC(Ph)(n-C18H37N) (Compound 8)

(89) To a solution of 2-octadecylisoindolin-1-imine (0.385 g, 1.00 mmol) in toluene (30 ml) was added methyl magnesium bromide solution (1M in Bu.sub.2O, 1.00 mL, 1.00 mmol) at 0 C. It was allowed to warm to room temperature and the solution was transferred with a cannula to another flask containing a solution of pentamethylcyclopentadienyl titanium trichloride (0.289 g, 1.00 mmol) in toluene (30 mL). The reaction was heated up to 50 C. and stirred for 72 h. The solution was filtered off, the filtrate was concentrated to approx. 5 mL. The flask was stored at 80 C. After 2 days remaining liquid was removed by decantation and resulting solid was dried under reduced pressure to yield the product as a yellow powder (milligram quantities, <5%).

(90) The powder was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 0.92 (t, 3H); 1.38 (m, 32H); 2.21 (s, 15H); 3.32 (m, 2H); 3.48 (t, 2H); 6.82 (d, 1H); 7.02 (m, 2H); 7.95 (m, 1H).

(91) ##STR00033##

Synthesis of the 2-cyclooctyl-7-fluoroisoindolin-1-imine hydrobromide (Ligand 9)

(92) To a solution of 2-(bromomethyl)-6-fluorobenzonitrile (1.50 g, 7.01 mmol) in toluene (40 ml) a solution of cyclooctylamine (0.892 g, 7.01 mmol) in toluene (20 ml) was added dropwise within 20 min. if was stirred at 50 C. overnight. The solution was concentrated to approx. 10 mL, diethylether (40 ml) was added (40 mL) and filtered off. It was washed with diethylether (320 ml), dried under reduced pressure to yield the product as a white solid (0.567 g, 1.88 mmol, 24%).

(93) The powder was characterized by .sup.1H NMR (300 MHz) (CDCl.sub.3) (ppm): 1.55-2.12 (m, 14H); 4.81 (s, 2H); 5.25 (m, 1H); 7.09 (s, 1H); 7.30 (d, 1H); 7.42 (d, 1H); 7.73 (m, 1H); 11.26 (s, 1H).

(94) ##STR00034##

Synthesis of Me5CpTiCl2(NC(7-fluoro-Ph)(c-C8H15N) (Compound 9)

(95) To a solution of pentamethylcyclopentadienyl titanium trichloride (0.466 g, 1.61 mmol) and 2-cyclooctyl-7-fluoroisoindolin-1-imine hydrobromide

(96) (0.550 g, 1.61 mmol) in toluene (40 ml) was added triethylamine (0.550 mL, 4.00 mmol). The reaction was heated up to 50 C. and stirred for 7 d. The solution was filtered off, the filtrate was concentrated to approx. 5 mL and hexane was added (50 mL). It was filtered off and dried under reduced pressure to yield the product as a yellow powder (508 mg, 0.986 mmol, 61%).

(97) The powder was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 1.19-1.69 (m, 14H); 2.23 (s, 15H); 3.48 (s, 2H); 4.48 (m, 1H); 8.50 (d, 1H); 6.64 (m, 1H); 6.83 (m, 1H), .sup.19F NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 113.93 and .sup.13C NMR (75 MHz) (C.sub.6D.sub.6) (ppm): 140.0; 132.7; 129.1; 127.8; 118.6; 116.0; 53.7; 47.7; 32.4; 27.3; 25.9; 25.2; 13.6.

(98) ##STR00035##

Synthesis of Me5CpTiCl2(NC(7-fluoro-Ph)(c-C8H15N) (Compound 9M)

(99) To a solution of Compound 9 (350 mg, 0,682 mmol) in toluene (40 ml) was added methyl magnesium chloride solution (3M in THF, 0.680 ml, 2.04 mmol) dropwise at 80G. Mixture was allowed to warm to room temperature and stirred overnight. Trimethylsilyl chloride (0.100 ml) was added dropwise and the reaction was stirred for 1 hour. The mixture was concentrated and hexane was added (50 ml). If was filtered off and dried under reduced pressure to yield the product as a yellow powder (84 mg, 0.178 mmol, 27%).

(100) The powder was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 0.73 (s, 6H); 1.32-1.65 (m, 14H); 2.12 (s, 15H); 3.71 (s, 2H); 4.58 (m, 1H); 6.60 (d, 1H); 6.68 (d, 1H); 8.88 (m, 1H), 19F NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 118.27 and .sup.13C NMR (75 MHz) (C.sub.6D.sub.6) (ppm): 144.1; 131.8; 120.5; 118.8; 115.8; 115.6; 52.1; 47.5; 47.1; 32.3; 27.4; 26.1; 25.5; 12.6.

(101) ##STR00036##

Synthesis of 1-cyclooctylpyrrolidin-2-imine (Ligand 10)

(102) 4-Bromobutyronitrile (0.740 g, 5.00 mmol) and cyclooctylamine (0.636 g, 5.00 mmol) were mixed without solvent and heated to 100 C. overnight. The reaction mixture became solid. It was dissolved in dichloromethane (20 ml) and diethylether was added (50 mL). It was filtered off and washed with diethylether (225 mL). Again it was dissolved in dichloromethane (40 mL) and dried over MgSO.sub.4. St was filtered off and dried under reduced pressure to yield the hydrobromide salt of the product as a white powder (380 mg, 1.38 mmol, 28%).

(103) The hydrobromide salt of Ligand 10 was neutralized due to poor solubility in toluene and therefore low reactivity in the next step. Neutralization was performed according to the following procedure:

(104) Hydrobromide salt of Ligand 10 (1.300 g, 4.72 mmol) was added to an aqueous solution of sodium hydroxide (4.30 g NaOH in 100 ml H.sub.2O). The mixture was stirred for 10 minutes. It was extracted with diethylether (350 mL), the combined organic phase was dried over MgSO.sub.4, filtered and the solvent removed under reduced pressure to yield the product as a light yellow solid (0.69 g, 3.54 mmol, 75%).

(105) The powder was characterized by .sup.1H NMR (300 MHz) (CDCl.sub.3) (ppm): 1.43-1.76 (m, 14H); 2.90 (m, 2H); 2.41 (m, 1H); 2.56 (t, 2H); 3.36 (t, 2H); 4.15 (s, 1H).

(106) ##STR00037##

Synthesis of (Me5Cp)(1-cyclooctylpyrrolidine-2-iminato)TiCl2 (Compound 10)

(107) To a solution of pentamethylcyclopentadienyl titanium trichloride (1.042 g, 3.60 mmol) and Ligand 10 (700 mg, 3.60 mmol) in toluene (30 mL) was added triethylamine (1.25 mL, 9.00 mmol). The reaction was heated up to 50 C. and stirred for 72 h. The solution was filtered off, the filtrate was concentrated to approx. 5 mL and hexane (20 mL) was added. The flask was stored at 80 C. overnight and filtered off. It was recrystallized from toluene/hexanes to yield the product (65 mg, 0.144 mmol, 4% yield).

(108) The powder was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 1.08 (m, 2H); 1.20 (m, 2H); 1.35-1.64 (m, 14H); 2.15 (s, 15H); 2.54 (t, 2H); 4.21 (m, 1H),

(109) ##STR00038##

Synthesis of 2-propylisoindolin-1-imine (Ligand 11)

(110) Propylamine (4.11 ml, 50.0 mmol) was added to a solution of 4-Bromomethylbenzonitrile (9.80 g, 50.0 mmol) in toluene (70 ml) and heated to 50 C. overnight. A white solid was filtered off and washed with toluene (40 ml), followed by hexanes (60 ml). It was dried for 12 hours under reduced pressure, yielding the hydrobromide salt of the product as a white powder (10.9 g, 47.7 mmol, 85%).

(111) Due to presence of unreacted propylamine (observable by NMR), a neutralization procedure performed.

(112) 2-propylisoindolin-1-imine hydrobromide (12.0 g, 47.0 mmol) of was added to an aqueous solution of sodium hydroxide (9.41 g in 100 ml H.sub.2O). The organic phase was removed and further extracted from the aqueous layer using washings of diethylether (450 mL). The combined organic phase was then dried over MgSO.sub.4, filtered and all volatiles were removed. An oil was formed. Hexanes (10 mL) was added to encourage precipitation but still no solid precipitate formed. Solvent was removed under reduced pressure overnight. The product was dried for another 18 h using molecular sieves. The molecular sieves were decanted off and the solvent evacuated under reduced pressure. Diethylether (15 mL) was added and stirred overnight. Volatiles were removed under reduced pressure and followed by a second washing with diethylether (15 ml) yielding the product as pale pink/purple powder (4.09 g, 23.5 mmol, 50%).

(113) The powder was characterized by .sup.1H NMR (300 MHz) (CDCl.sub.3) (ppm): 7.80 (d, 1H); 7.41-7.30 (m, 3H); 8.20 (s, 1H); 4.35 (s, 2H); 3.45 (t, 2H); 1.71-1.58 (m, 2H); 0.90 (t, 3H),

(114) ##STR00039##

Synthesis of Me5CpTiCl2(NC(Ph)(n-C3H7N) (Compound 11)

(115) Triethylamine (1.93 ml, 13.8 mmol) was added to solution of 2-propylisoindolin-1-imine (0.600 g, 3.45 mmol) and pentamethylcyclopentadienyl titanium trichloride (1.00 g, 3.45 mmol) in toluene (60 ml). It was heated to 80 C. for 72 h. The triethylamine salts were filtered and toluene removed leaving an orange/brown wax-like precipitate. The precipitate was washed with hexanes (80 mL) to aid the removal of excess toluene. All volatiles were then removed under reduced pressure to yield the product as a yellow powder (0.750 g, 1.76 mmol, 51%).

(116) The powder was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 7.88-7.85 (m, 1H); 7.09-7.02 (m, 2H); 6.87-6.84 (m, 1H); 3.52 (s, 2H); 3.21 (t, 2H); 2.17 (s, 15H); 1.40-1.28 (m, 2H); 0.80 (t, 3H) and .sup.13C NMR (75 MHz) (C.sub.6D.sub.6) (ppm): 160.7; 141.0; 134.7; 131.0; 128.9; 124.6; 122.7; 52.0; 46.4; 22.2; 13.2; 11.5.

(117) ##STR00040##

Synthesis of 2-butylisoindolin-1-imine hydrobromide (Ligand 12)

(118) Butylamine (2.47 ml, 25.0 mmol) was added to a solution of 2-Bromomethylbenzonitrile (4.90 g (25.0 mmol) in toluene (70 ml) and heated to 50 C. overnight. The white solid was filtered and washed with toluene (100 ml), followed by hexane (80 ml). It was dried for 12 hours under reduced pressure, yielding the product as a light yellow powder (5.38 g, 20.0 mmol, 80%).

(119) The powder was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 10.25 (br s, 1H); 9.78 (br s, 1H); 9.01 (d, 1H); 7.89-7.51 (m, 3H); 4.73 (s, 2H); 4.20 (t, 2H); 1.86-1.78 (m, 2H); 1.61-1.49 (m, 2H); 0.98 (t, 3H).

(120) ##STR00041##

Synthesis of Me5CpTiCl2(NC(Ph)(n-C3H7N) (Compound 12)

(121) Triethylamine (1.00 ml, 7.43 mmol) was added to solution of 2-butylisoindolin-1-imine (0.500 g, 1.86 mmol) and pentamethylcyclopentadienyl titanium trichloride (0.54 g, 1.86 mmol) in toluene (35 ml) It was heated to 50 C. overnight. The triethylamine salts were filtered off and all volatiles were then removed under reduced pressure. It was washed with hexanes and dried under reduced pressure to yield the product as a yellow powder (0.64 g, 1.45 mmol, 78%).

(122) The powder was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 7.90-7.87 (m, 1H); 7.08-7.04 (m, 2H); 6.87-6.84 (m, 1H); 3.52 (s, 2H); 3.24 (t, 2H); 2.18 (s, 15H); 1.34-1.18 (m, 4H); 0.89 (t, 3H) and .sup.13C NMR (75 MHz) (C.sub.6D.sub.6); 160.7; 141.0; 134.7; 131.0; 128.3; 126.9; 124.6; 122.8; 52.1; 44.9; 30.9; 20.6; 14.1; 13.3.

(123) ##STR00042##

Synthesis of 2-allylisoindolin-1-imine hydrobromide (Ligand 13)

(124) Allylamine (1.13 ml, 15.0 mmol) was added to a solution of 2-(bromomethyl) benzonitrile (2.94 g, 15.0 mmol) in toluene (20 ml). The solution was heated to 50 C. for 72 hours. The white solid was filtered off, washed with toluene (30 ml), followed by hexanes (30 ml) and dried in vacuo to yield the product as a white powder (3.59 g, 14.2 mmol, 95%).

(125) The powder was characterized by .sup.1H NMR (300 MHz) (CDCl.sub.3) (ppm); 10.34 (br s, 1H); 9.79 (br s, 1H); 8.99-8.97 (d, 1H); 7.89-7.51 (m, 3H); 6.00-5.93 (ddt, 1H); 5.44-5.38 (dds 1H); 5.39-5.36 (dd, 1H); 4.85-4.83 (d, 2H); 4.74 (s, 2H).

(126) ##STR00043##

Synthesis of Me5CpTiCl2(NC(Ph)(n-allylamine) (Compound 13)

(127) Triethylamine (2.20 ml, 15.8 mmol) was added to a solution of 2-allylisoindolin-1-imine hydrobromide (1.00 g, 3.95 mmol) and pentamethylcyclopentadienyl titanium trichloride (1.14 g, 3.95 mmol) in toluene (60 ml). The mixture was heated to 50 C. overnight. Whilst maintaining an inert atmosphere, the triethylamine salts (yellow precipitate) were filtered off leaving an orange/red liquid containing the catalyst product. Toluene was removed under reduced pressure to yield the product as a yellow powder (0.540, 1.27 mmol, 32%), The powder was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm); 7.85-7.82 (dd, 1H); 7.07-7.02 (m, 2H); 6.86-6.83 (d, 1H); 5.57-5.52 (ddt, 1H); 4.96-4.93 (dd, 1H); 4.96-4.90 (dd, 1H); 3.91-3.89 (d, 2H); 3.56 (s, 2H); 2.18 (s, 15H) and .sup.13C NMR (75 MHz) (C.sub.6D.sub.6) (ppm) 170.4; 141.1; 134.4; 133.2; 131.1; 128.3; 127.3; 124.6; 122.8; 117.8; 51.7; 47.1; 13.3.

(128) ##STR00044##

Synthesis of Me4PhCpTiCl2(MC(Ph)(n-allylamine) (Compound 14)

(129) Triethylamine (1.10 ml, 7.90 mmol) was added to a solution of 2-allylisoindolin-1-imine hydrobromide (0.50 g, 1.98 mmol) and tetramethylphenylcyclopentadienyl titanium trichloride (0.69 g, 1.98 mmol) in toluene (40 ml). The mixture was heated to 50 C. overnight. The solution was then filtered to remove triethylamine salts and the toluene was removed under reduced pressure. The product was then re-extracted in hexanes (60 ml) and back filtered, yielding the product as a bright yellow powder (0.480 g, 0.99 mmol, 50%).

(130) The powder was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 7.84-7.80 (m, 1H); 7.73-7.70 (m, 2H); 7.24-6.98 (m, 5H); 6.73-6.70 (m, 1H); 5.42-5.29 (ddt, 1H); 4.88-4.84 (dd, 1H); 4.83-4.76 (dd, 1H); 3.76-3.74 (d, 2H); 3.36 (s, 2H); 2.34 (s, 6H); 2.23 (s, 8H) and .sup.13C NMR (75 MHz) (C.sub.6D.sub.6) (ppm) 160.5; 141.1; 135.6; 134.4; 133.1; 132.1; 131.3; 131.1; 128.3; 128.2; 127.2; 126.6; 125.0; 122.6; 118.0; 51.6; 47.3; 14.5; 13.4.

(131) ##STR00045##

Synthesis of 2-homoallylisoindolin-1-imine hydrobromide (Ligand 15)

(132) But-3-en-1-amine (2.30 ml, 25.0 mmol) was added to a solution of 2-(bromomethyl) benzonitrile (4.90 g, 25.0 mmol) in toluene (70 ml). On addition of the amine, the solution immediately turned from colourless to dark green. The mixture was heated to 50 C. for 72 hours in which a white precipitate (in a pale pink solution) was formed. The precipitate was then filtered and washed with toluene (280 ml), followed by hexanes (80 ml). Solvent was removed under reduced pressure to yield the product as a white powder (4.81 g, 18.0 mmol, 72%).

(133) The powder was characterized by .sup.1H NMR (300 MHz) (CDCl.sub.3) (ppm): 10.21 (br s, 1H); 9.77 (br s, 1H); 8.96-8.94 (d, 1H); 7.69-7.50 (m, 3H); 6.08-5.94 (ddt, 1H); 5.18-5.07 (m, 2H); 4.76 (s, 2H); 4.28-4.24 (t, 2H); 2.67-2.60 (q, 1H),

(134) ##STR00046##

Synthesis of Me5CpTiCl2(NC(Ph)(n-homoallylamine) (Compound 15)

(135) Triethylamine (1.50 ml, 10.7 mmol) was added to a solution of 2-homoallylisoindolin-1-imine hydrobromide (0.50 g, 2.68 mmol) and pentamethylcyclopentadienyl titanium trichloride (0.78 g, 2.68 mmol) in toluene (40 ml) and heated to 50 C. overnight. Filtration of the triethylamine salts was performed, followed by evaporation of toluene in under reduced pressure.

(136) A purification procedure was then performed by dissolving the product in small amount of toluene (15 ml) and adding around 100 ml of hexanes to other side of double schlenk. Reduced pressure was then applied and the set up was left (without stirring) overnight. Diffusion of around 40 ml of hexanes to the schlenk containing the catalyst product occurred, yielding more yellow precipitate. The precipitate was back filtered and evaporated to dryness yielding the product as a yellow powder (0.360 g, 0.820 mmol, 30%).

(137) The powder was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 7.88-7.86 (m, 1H); 7.07-7.03 (m, 2H); 6.85-6.83 (m, 1H); 5.79-5.65 (ddt, 1H); 5.10-5.04 (dds 1H); 4.99-4.95 (dd, 1H); 3.53 (s, 2H); 3.35-3.30 (t, 2H); 2.17 (s, 15H) and .sup.13C NMR (75 MHz) (C.sub.6D.sub.6) (ppm) 160.7; 141.0; 135.3; 134.6; 131.0; 127.1; 124.6; 122.7; 117.4; 52.2; 44.3; 33.2; 13.3.

(138) ##STR00047##

Synthesis of (E)-2-(But-2-en-1yl)isoindolin-1-imine hydrobromide (Ligand 16)

(139) (E) But-2en-1-amine (1.78 g, 25.0 mmol) was added to a solution of 2-(bromomethyl) benzonitrile (4.90 g, 25.0 mmol) in toluene (70 ml). The solution was heated to 50 C. overnight. A white precipitate formed which was filtered (maintaining an inert atmosphere) and washed with hexanes (20 ml) to yield the product as a white powder (5.88 g, 22.0 mmol, 88%).

(140) The powder was characterized by .sup.1H NMR (300 MHz) (CDCl.sub.3) (ppm): 10.20 (br s, 1H); 9.66 (br s, 1H); 8.87-8.85 (d, 1H): 7.67-7.48 (m, 3H); 6.03-5.88 (m, 1H); 5.75-5.59 (m, 1H); 4.70-4.89 (m, 4H); 1.78-1.73 (d, 3H),

(141) ##STR00048##

Synthesis of Me5CpTiCl2(NC(Ph)((E)-2-(but-2en-1-amine)) (Compound 16)

(142) Triethylamine (1.04 ml, 7.49 mmol) was added to a solution of (E)-2-(But-2en-1yl)isoindolin-1-imine hydrobromide (0.500 g, 1.87 mmol) and penta-methylcyclopentadienyl titanium trichloride (0.540 g, 1.87 mmol) in toluene (40 ml) and heated to 50 C. overnight. The triethylamine salts were removed by filtration and the toluene was removed under reduced pressure. The yellow precipitate was then washed with hexanes (30 mi) and dried under reduced pressure to yield the product as a yellow powder (0.220 g, 0.500 mmol, 27%).

(143) The powder was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 7.88-7.85 (m, 1H); 7.07-7.01 (m, 2H); 6.85-6.82 (m, 1H); 5.46-5.35 (m, 1H); 5.31-5.22 (m, 1H); 3.90-3.88 (d, 2H); 3.56 (s, 2H); 2.17 (s, 15H); 1.50-1.48 (dd, 3H) and 13C NMR (75 MHz) (C.sub.6D.sub.6) (ppm) 160.3; 141.1; 134.8; 131.1; 130.0; 128.3; 127.1; 126.0; 124.6; 122.8; 51.6; 46.6; 17.7; 13.3.

(144) ##STR00049##

(145) Part II. Batch EP Copolymerisation Examples and Comparative Experiments

(146) The batch co-polymerizations were carried out in a 2-liter batch autoclave equipped with a double intermig and baffles. The reaction temperature was set on 90 C.+/3 C. (data shown In Table 1 and 2) (120+3 C. for reactions in Table 3) and controlled by a Lauda Thermostat. The feed streams (solvents and monomers) were purified by contacting with various adsorption media to remove catalyst killing impurities such as water, oxygen and polar compounds as is known to those skilled in the art. During polymerisation the ethylene and propylene monomers were continuously fed to the gas cap of the reactor. The pressure of the reactor was kept constant by a back-pressure valve.

(147) In an inert atmosphere of nitrogen, the reactor was filled with pentamethylheptanes (PMH) (950 ml), MAO (Chemtura, 10 wt. % Al in toluene diluted to 0.10 M), and BHT (Sigma Aldrich 0.2 M in hexanes). The reactor was heated to 90 (data shown in Table 1 and 2) (120 C. for reactions In Table 3), while stirring at 1350 rpm. The reactor was pressurized to 7 bar and conditioned under a determined ratio of ethylene, propylene. After 15 minutes, the catalyst components were added into the reactor and the catalyst vessel was rinsed with PMH (50 mL) subsequently. After 10 minutes of polymerisation, the monomer flow was stopped and the solution was carefully dumped in an Erlenmeyer flask of 2 L, containing a solution of Irganox-1076 in iso-propanol and dried over night at 100 C. under reduced pressure. The polymers were analysed for intrinsic viscosity (IV), for molecular weight distribution (SEC-DV) and composition (FT-IR).

(148) The experimental results are given in Table 1, 2 and 3.

(149) TABLE-US-00001 TABLE 1 Cocatalyst Polymer Analysis Metal complex BHT MAO-10T C2 C3 IV Experiment Name mol mol/l mol/l wt % wt % dl/g Comparative Compound AM 0.05 900 450 52.6 47.4 7.5 Example 1 Comparative Compound B 0.07 900 450 46.0 54.0 6.4 Example 2 Comparative Compound BM 0.05 900 450 7.0 Example 3 Comparative Compound CM 0.07 900 450 44.2 55.8 6.8 Example 4 Inventive Compound 4M 0.14 900 450 39.7 60.3 8.5 Example 1 Inventive Compound 6M 0.20 900 450 36.7 61.3 7.8 Example 2 Inventive Compound 2M 0.14 900 450 38.4 61.6 6.2 Example 3 Inventive Compound 8 0.14 900 450 40.7 59.3 6.7 Example 4 Inventive Compound 11 0.30 900 450 42 59 9.0 Example 5 Inventive Compound 12 0.30 900 450 42 58 9.9 Example 6 Inventive Compound 9M 0.14 900 450 35.2 64.8 8.8 Example 7 Inventive Compound 1M 0.30 900 450 44.0 56.0 8.0 Example 8 Inventive Compound 3M 0.20 900 450 37.4 62.6 8.3 Example 9 10 min reaction time, 90 C., 7 barg, propylene 400 NL/h, ethylene 200 NL/h

(150) TABLE-US-00002 TABLE 2 Cocatalyst Polymer Analysis Metal complex BHT MAO-10T C2 C3 IV SEC-DV universal calibration Experiment Name mol mol/l mol/l wt % wt % dl/g Mn Mw Mz Mw/Mn Comparative Compound AM 0.05 900 450 52.6 47.4 7.5 341 680 1140 2.0 Example 1 Comparative Compound BM 0.05 900 450 7.0 304 649 1037 2.1 Example 3 Comparative Compound CM 0.07 900 450 44.2 55.8 6.8 290 652 1129 2.2 Example 4 Inventive Compound 4M 0.14 900 450 39.7 60.3 8.5 381 809 1435 2.1 Example 1 Inventive Compound 6M 0.20 900 450 38.7 61.3 7.8 334 705 1190 2.1 Example 2 Inventive Compound 2M 0.14 900 450 38.4 61.6 8.2 387 857 1636 2.2 Example 3 10 min reaction time, 90 C., 7 barg, propylene 400 NL/h, ethylene 200 NL/h

(151) TABLE-US-00003 TABLE 3 Cocatalyst Polymer Analysis Metal Complex BHT MAO-10T C2 C3 IV Experiment Name mol mol/l mol/l wt % wt % dl/g Comparative Compound AM 0.05 900 450 51.5 48.5 4.1 Example Inventive Compound 4M 0.10 900 450 41.9 58.2 4.6 Example 1 Inventive Compound 2M 0.10 900 450 42.8 57.2 5.0 Example 2 Inventive Compound 1M 0.10 900 450 43.0 57.0 4.6 Example 3 Inventive Compound 3M 0.10 900 450 42 58 5.1 Example 4 10 min reaction time, 120 C., 7 barg, propylene 400 NL/h, ethylene 140 NL/h

(152) Part III. Batch EPDM Tetropolymerisations (General Procedure)

(153) The batch terpolymerizations were carried out in a 2-liter batch autoclave equipped with a double intermig and baffles. The reaction temperature was set on 90 C. and controlled by a Lauda Thermostat. The feed streams (solvents and monomers) ware purified by contacting with various absorption media to remove catalyst killing impurities such as water, oxygen and polar compounds as is known to those skilled in the art. During polymerisation the ethylene and propylene monomers were continuously fed to the gas cap of the reactor. The pressure of the reactor was kept constant by a back-pressure valve.

(154) In an inert atmosphere of nitrogen, the reactor was filled with pentamethylheptanes PMH (950 mL), MAO-10T (Crompton, 10 wt % in toluene), BHT and 5-ethylidene-2-norbonene (ENB, 2.8 ml). The reactor was heated to 90 C., while stirring at 1350 rpm. The reactor was pressurized and conditioned under a determined ratio of ethylene, propylene and hydrogen (0.35 NL/h). After 15 minutes, the catalyst components were added into the reactor and the catalyst vessel was rinsed with PMH (50 ml) subsequently. After 10 minutes of polymerisation, the monomer flow was stopped and the solution was carefully dumped in an Erlenmeyer flask of 2 L, containing a solution of Irganox-1076 in iso-propanol and dried over night at 100 C. under reduced pressure.

(155) The polymers were analysed for composition (FT-IR).

(156) The experimental results are given in Table 4.

(157) TABLE-US-00004 TABLE 4 Cocatalyst Polymer Analysis Metal complex BHT MAO-10T C2 C3 ENB Experiment Name mol mol/l mol/l wt % wt % wt % Comparative Compound AM 0.10 900 450 49.1 47.2 3.73 Example 1 Comparative Compound CM 0.07 900 450 44.9 51.2 4.00 Example 2 Inventive Compound 2M 0.14 900 450 40.5 54.8 4.78 Example 1 Inventive Compound 8 0.14 900 450 35.4 59.7 4.94 Example 2 Inventive Compound 11 0.30 900 450 37.6 57.3 5.11 Example 3 Inventive Compound 12 0.30 900 450 40.8 54.0 5.17 Example 4 Inventive Compound 1M 0.40 900 450 38.7 56.0 5.22 Example 5 Inventive Compound 3M 0.20 900 450 38.5 56.5 5.01 Example 6 Inventive Compound 10 0.10 900 450 47.9 46.0 6.16 Example 7 10 min reaction time, 90 C., 7 barg, propylene 400 NL/h, ethylene 200 NL/h, hydrogen 0.35 NL/h

(158) Results:

(159) Due to the fact that more catalyst leads to more heat formation the used reactor that was optimized to run at 90 C.+/3 C. (see tables 1, 2 and 3) and at 120 C.+/3 C. (see table 4) the amount of catalyst was chosen to give a heat formation in this respective range. Even though the catalyst amount might be different the data can be used to establish certain results.

(160) The parameter to look at are preferably the IV and Mw values as they show what molecular weight magnitudes were achievable. As higher temperatures normally give a lower IV and Mw value the above mentioned lower amount of catalyst in order to limit the temperature to about 90 C. and 120 C. respectively would in ease of the same amount lead to higher temperatures which give lower IV and Mw values which would even amplify this effect rather than to compensate this effect.

(161) The inventive compounds lead to higher IV and Mw values than the comparative examples.