Metal complex with a bridged cyclopentadienyl amidine ligand

Abstract

The present invention relates to a new metal complex of the formula (1) ##STR00001## wherein: M is a group 4-6 metal R.sup.1 means is a substituent comprising a heteroatom of group 15, through which R.sup.1 is bonded to the imine carbon atom; R.sup.2-R.sup.5 are the same or different and each represents a hydrogen atom, an optionally substituted C1-10 alkyl group, an optionally substituted C1-10 alkoxy group, an optionally substituted C6-20 aryl group, an optionally substituted C6-20 aryloxy group, an optionally substituted C7-20 aralkyl group, an optionally substituted C7-20 aralkyloxy group, a silyl group substituted with optionally substituted C1-20 hydrocarbon group(s), a C1-20 hydrocarbon-substituted amino group or the adjacent R.sup.2-R.sup.5 may be linked to each other to form a ring; R.sup.6-R.sup.9 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, an optionally substituted C6-20 aryl group, an optionally substituted C6-20 aryloxy group, an optionally substituted C7-20 aralkyl group, an optionally substituted C7-20 aralkyloxy group, a silyl group substituted with optionally substituted C1-20 hydrocarbon group(s), a C1-20 hydrocarbon-substituted amino group or the adjacent R.sup.6-R.sup.9 may be linked to each other to form a ring; L is an optional neutral Lewis basic ligand, and j is an integer denoting the number of neutral ligands L; and X Is an anionic ligand, and r is an integer denoting the number of anionic ligands X.

Claims

1. A metal complex of the formula (1) ##STR00018## wherein: M is a group 4-6 metal; R.sup.1 is a substituent comprising a heteroatom of group 15, and R.sup.1 is bonded to the imine carbon atom via the heteroatom; R.sup.2-R.sup.5 are the same or different, and each of R.sup.2, R.sup.3, R.sup.4 and R.sup.5 represents a hydrogen atom, an optionally substituted C1-10 alkyl group, an optionally substituted C1-10 alkoxy group, an optionally substituted C6-20 aryl group, an optionally substituted C6-20 aryloxy group, an optionally substituted C7-20 aralkyl group, an optionally substituted C7-20 aralkyloxy group, a silyl group substituted with at least one optionally substituted C1-20 hydrocarbon group, or a C1-20 hydrocarbon-substituted amino group, and adjacent ones of R.sup.2, R.sup.3, R.sup.4 and R.sup.5 may be linked to each other to form a ring; R.sup.6-R.sup.9 are the same or different, and each of R.sup.6, R.sup.7, R.sup.8 and R.sup.9 represents a hydrogen atom, a halogen atom, an optionally substituted C1-10 alkyl group, an optionally substituted C1-10 alkoxy group, an optionally substituted C6-20 aryl group, an optionally substituted C6-20 aryloxy group, an optionally substituted C7-20 aralkyl group, an optionally substituted C7-20 aralkyloxy group, a silyl group substituted with at least one optionally substituted C1-20 hydrocarbon group a C1-20 hydrocarbon-substituted amino group and adjacent ones of R.sup.6, R.sup.7, R.sup.8 and R.sup.9 may be linked to each other to form a ring; L is a neutral ligand, and j is an integer denoting the number of neutral ligands L, wherein j is 0 to n, with n being an amount that satisfies 18 electrons of valance shells of the metal M; and X is an anionic ligand, and r is an integer denoting the number of anionic ligands X to provide charge neutrality.

2. The metal complex according to claim 1, wherein M is selected from the group consisting of Ti, Zr and Hf.

3. The metal complex according to claim 1, wherein R.sup.2-R.sup.5 are the same or different and each represents a hydrogen atom or a C1-5 alkyl group.

4. The metal complex according to claim 1, wherein the heteroatom of group 15 is a nitrogen atom, through which R1 is bonded to the imine carbon atom.

5. The metal complex according to claim 1, wherein X represents 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, wherein if r is greater than 1, each X is independently of any other X one of the specified substituents.

6. The metal complex according to claim 1, wherein j is zero.

7. The metal complex according to claim 1, wherein each of R.sup.6, R.sup.7, R.sup.8 and R.sup.9 is a hydrogen atom.

8. The metal complex according to claim 1, wherein: the heteroatom of group 15 is a nitrogen atom, through which R1 is bonded to the imine carbon atom, and R.sup.1 is of the general formula NR.sup.10R.sup.11 with R.sup.10 and R.sup.11 being individually selected from the group of aliphatic C1-10 hydrocarbyl, halogenated aliphatic C1-10 hydrocarbyl, aromatic C6-20 hydrocarbyl, and halogenated C6-20 aromatic hydrocarbonyl residues, and R.sup.10 and R.sup.11 may be linked to each other to form a ring, or one of R.sup.10 and R.sup.11 may be linked with any one of the radicals R.sup.6 to R.sup.9 to form a ring; M is selected from the group consisting of Ti, Zr and Hf; R.sup.2-R.sup.5 are the same or different and each represents a hydrogen atom or a C1-5 alkyl group; X represents 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, wherein if r is greater than 1, each X is independently of any other X one of the specified substituents; j is zero; and each of R.sup.6, R.sup.7, R.sup.8 and R.sup.9 is a hydrogen atom.

9. The metal complex according to claim 8, wherein: R.sup.1 is dimethylamide, diisopropylamide, dicyclohexylamide, or N-dimethylphenyl N-ethylamide; M is Ti; X is Cl or methyl; and each of R.sup.2, R.sup.3, R.sup.4 and R.sup.5 is methyl.

10. A process for producing the metal complex represented by the formula (I) according to claim 1, the process comprising reacting a substituted cyclopentadiene compound of the formula (2) ##STR00019## with a metal compound represented by the formula (3)
MX.sub.(r+2)L.sub.j(3).

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

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

13. The catalyst system according to claim 11, wherein the activator b) is at least one of a borane, a borate, or an organoaluminum compound.

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

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

16. 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 selected from the group consisting of 5-methylene-2-norbornene 5-ethylidene-2-norbornene, 5-vinylnorbornene, 2,5-norbornadiene, dicyclopentadiene and vinylcyclohexene.

17. A compound of the formula (2) ##STR00020## wherein: R.sup.1 is a substituent comprising a heteroatom of group 15, and R.sup.1 is bonded to the imine carbon atom via the heteroatom; R.sup.2-R.sup.5 are the same or different, and each of R.sup.2, R.sup.3, R.sup.4 and R.sup.5 represents a hydrogen atom, an optionally substituted C1-10 alkyl group, an optionally substituted C1-10 alkoxy group, an optionally substituted C6-20 aryl group, an optionally substituted C6-20 aryloxy group, an optionally substituted C7-20 aralkyl group, an optionally substituted C7-20 aralkyloxy group, a silyl group substituted with at least one optionally substituted C1-20 hydrocarbon group, or a C1-20 hydrocarbon-substituted amino group, and adjacent ones of R.sup.2, R.sup.3, R.sup.4 and R.sup.5 may be linked to each other to form a ring; and R.sup.6-R.sup.9 are the same or different, and each of R.sup.6, R.sup.7, R.sup.8 and R.sup.9 represents a hydrogen atom, a halogen atom, an optionally substituted C1-10 alkyl group, an optionally substituted C1-10 alkoxy group, an optionally substituted C6-20 aryl group, an optionally substituted C6-20 aryloxy group, an optionally substituted C7-20 aralkyl group, an optionally substituted C7-20 aralkyloxy group, a silyl group substituted with at least one optionally substituted C1-20 hydrocarbon group, a C1-20 hydrocarbon-substituted amino group and adjacent ones of R.sup.6, R.sup.7, R.sup.8 and R.sup.9 may be linked to each other to form a ring.

18. A process for the manufacturing of a compound of the formula (2) according to claim 17, the process comprising reacting at least one of a nitrile of formula (4) and an oxime of formula (5) ##STR00021## with at least one of an organic lithium compound LiR.sup.1 and an organic magnesium compound Mg(Hal)R.sup.1 wherein R.sup.10 represents a hydrogen atom, an optionally substituted C1-10 alkyl group, an optionally substituted C6-20 aryl group, an optionally substituted C7-20 aralkyl group, or a silyl group optionally substituted with at least one optionally substituted C1-20 hydrocarbon, and Hal means a halide.

Description

FIGURES

(1) FIG. 1 shows the X-ray structure of compound 2

(2) FIG. 2 shows the X-ray structure of compound 3

(3) FIG. 3 shows the X-ray structure of compound 5

(4) FIG. 4 shows the X-ray structure of compound 6

(5) FIG. 5 shows the X-ray structure of compound 8

(6) FIG. 6 shows the X-ray structure of compound 9

SYNTHESIS OF COMPOUNDS FOR THE COMPARATIVE EXAMPLES

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

Synthesis of Me5CpTiMe2(NC(Ph)(iPr2N)) (Compound B)

(8) 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, 4.40 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.

(9) ##STR00006##

(10) Compound C {.sup.5,.sup.1-C.sub.5Me.sub.4-2-C.sub.5H.sub.4C(.sup.tBu)N}TiCl.sub.2 was prepared as described in EP142637981, example 48.

(11) ##STR00007##
Compound D

(12) To a stirring hexanes solution (15 mL) of Compound C (0.27 g) was added dropwise two equivalents of MeMgCl (0.5 mL, 3.0 in THF). The solution rapidly turned from green to red with precipitation of colourless salts. After stirring for 2 h the volatiles were removed in vacuo and the resulting solid extracted in to hexanes and filtered. The hexanes were then removed in vacuo and the oily material carefully dried giving the desired product as a bright red waxy solid. Yield=0.065 g (27%). The compound was characterized by .sup.1H NMR (300 MHz) (C.sub.6D.sub.6) (ppm): 7.7 (d, 1H), 7.2 (d, 1H), 7.1 (dd, 1H) 7.0 (dd, 1H), 2.1 (s, 6H), 1.5 (s, 6H), 1.4 (s, 9H), 0.7 (s, 6H) and by .sup.13C-NMR (75.5 MHz) (CDCl.sub.3) (ppm): 186.0, 141.9, 138.4, 133.3, 133.0, 129.7, 129.3, 127.2, 126.5, 121.4, 51.5, 31.3, 31.1, 12.8, 12.1.

(13) ##STR00008##

Synthesis of Compounds for the Examples of the Invention

Synthesis of C5Me4H-2-C6H4C(NMe2)NH (Compound 1)

(14) ##STR00009##

(15) To a stirring THF (80 mL) solution of LiNMe.sub.2 (8.26 g, 162 mmol) cooled to 78 C. was added dropwise a solution of C.sub.5Me.sub.4H-2-C.sub.6H.sub.4CN (6.03 g, 27 mmol) in THF (60 mL). Following slow warming to RT, the solution had turned a very dark colour. The solution was then stirred at RT for a further 16 h after which time the solution had turned dark red. Toluene (100 mL) followed by water (200 mL) was added to quench the reaction, the aqueous phase was removed and the organic layer was dried over MgSO.sub.4. The solvent was removed in vacuo affording a viscous orange oil which was triturated with pentane and dried in vacuo giving a waxy orange solid. Yield=6.86 g (95%). .sup.1H NMR (major isomer (80%)) (CD.sub.2Cl.sub.2, 299.9 MHz, 243 K): 7.50-7.16 (4H, series of overlapping m, Ar), 3.16 (3H, as, NMe.sub.2)), 2.87 (1H, br q, CHMe, .sup.3J=7.1 Hz), 2.54 (3H, s, NMe.sub.2), 1.88 (3H, br s, CMeCMeCHMe), 1.84 (3H, br s, CHMeCMeCAr), 1.38 (3H, s, CMeCMeCAr), 0.79 (3H, d, CHMe, .sup.3J=7.1 Hz) ppm (NH not observed). .sup.13C-{.sup.1H} NMR (major isomer) (CD.sub.2Cl.sub.2, 75.4 MHz, 243 K): 166.3 (CN(NMe.sub.2)), 142.5 (CMeCMeCHMe), 140.6 (CHMeCMeCAr), 136.0 (CAr), 134.4 (CMeCMeCAr), 131.4 (Ar CH), 130.9 (Ar CH), 129.0 (1-C.sub.6H.sub.4 or 6-C.sub.6H.sub.4), 127.0 (Ar CH), 126.9 (Ar CH), 125.7 (6-C.sub.6H.sub.4 or 1-C.sub.5H.sub.4), 50.5 (CHMe), 40.4 (NMe.sub.2), 39.6 (NMe.sub.2), 15.0 (CHMe), 12.5 (CMeCMeCHMe), 12.0 (CMeCMeCAr), 11.2 (CHMeCMeCAr) ppm. IR (thin film, cm.sup.1): 3383 (s, u(NH)), 2957 (m), 2870 (m), 1632 (s), 1461 (m), 1453 (m), 1432 (w), 1349 (w), 1251 (s), 1128 (m), 1026 (m), 821 (m), 720 (s). FI-HRMS: m/z=268.1938 (calcd. for [C.sub.18H.sub.24N.sub.2].sup.+ m/z=268.1939).

Synthesis of {5,1-C5Me4-2-C6CH4C(NMe2)N}TiCl2 (Compound 2)

(16) ##STR00010##

(17) To a stirring toluene (40 mL) solution of Ti(NMe.sub.2).sub.4 (6.10 mL, 25.6 mmol) was added dropwise a toluene (20 mL) solution of C.sub.5Me.sub.4H-2-C.sub.6H.sub.4C(NMe.sub.2)NH (Compound 1) (6.86 g, 25.6 mmol). The solution immediately turned from orange to dark red and was stirred for a further 6 h at RT. The volatiles were then removed in vacuo and the solid extracted into toluene (40 mL). Trimethylsilyl chloride (7.10 mL, 56.3 mmol) was added dropwise and the solution was stirred for a further 16 h. The volatiles were again removed in vacuo and the dark red solid extracted into warm (ca. 50 C.) toluene (80 mL). The desired product crystallized after storage at 30 C. for two days. Following washing thoroughly with pentane (420 mL) and drying in vacuo the product was isolated as an orange microcrystalline powder. Yield=4.48 g (45%). .sup.1H NMR (CD.sub.2Cl.sub.2, 299.9 MHz, 293 K): 7.64-7.46 (4H, series of overlapping m, Ar), 3.34 (3H, s, NMe.sub.2), 3.14 (3H, s, NMe.sub.2), 2.19 (6H, s, CMeCMeCAr), 1.73 (6H, s, CMeCMeCAr) ppm. .sup.13C-{.sup.1H} NMR (CD.sub.2Cl.sub.2, 75.4 MHz, 293 K): 168.8 (CN), 138.7 (1-C.sub.6H.sub.4), 135.8 (6-C.sub.6H.sub.4), 132.0 (Ar CH), 131.3 (Ar CH), 130.7 (CMeCMeCAr), 128.7 (CMeCMeCAr), 127.7 (Ar CH), 127.5 (Ar CH), 125.1 (CAr), 41.7 (NMe.sub.2), 40.1 (NMe.sub.2), 13.1 (CMeCMeCAr), 12.4 (CMeCMeCAr) ppm. IR (NaCl plates, Nujol mull, cm.sup.1): 1573 (s), 1547 (s), 1269 (m), 1248 (m), 1206 (m), 1079 (w), 1019 (m), 953 (w), 918 (w), 880 (m), 823 (s), 774 (w), 760 (s), 712 (m), 673 (w), 595 (m), 536 (m). Anal. found (calcd. for C.sub.18H.sub.22Cl.sub.2N.sub.2Ti.0.1 (C.sub.7H.sub.8)): C, 56.98 (56.95); H, 5.82 (5.83); N, 7.02 (7.10) %. EI-MS: m/z=384 (30%, [M].sup.+), 340 (20%, [MNMe.sub.2].sup.+). Single crystals suitable for X-ray diffraction were grown from a benzene solution at room temperature.

Synthesis of {5,1-C5Me4-2-C6H4C(NMe2)N}TiMe2 (Compound 3)

(18) ##STR00011##

(19) To a stirring toluene (40 ml) solution of {.sup.5,.sup.1-C.sub.5Me.sub.4-2-C.sub.6H.sub.4C(NMe.sub.2)N}TiCl.sub.2 (Compound 2) (1.0 g, 2.60 mmol) was added dropwise two equivalents of MeMgCl (1.73 mL, 3.0 M in THF, 5.20 mmol). Following stirring for 16 h, the volatiles were removed in vacuo and the resulting solid extracted into pentane (420 mL). The desired complex was recrystallised from a concentrated pentane solution (20 mL) at 30 C. as a yellow-brown powder which was isolated and dried in vacuo. Yield=0.27 g (30%). .sup.1H NMR (C.sub.6D.sub.6, 299.9 MHz, 293 K): 7.29 (1H, d, 2-C.sub.6H.sub.4, .sup.3J=7.7 Hz), 7.09 (1H, dd, 3-C.sub.6H.sub.4, .sup.3J=7.7 Hz, 7.8 Hz), 6.95 (1H, dd, 4-C.sub.5H.sub.4, .sup.3J=6.5 Hz, 7.8 Hz), 6.93 (1H, d, 5-C.sub.6H.sub.4, .sup.3J=6.5 Hz), 2.65 (6H, s, NMe.sub.2), 2.19 (6H, s, CMeCMeCAr), 1.51 (6H, s, CMeCMeCAr), 0.60 (6H, s, TiMe) ppm. .sup.13C-{.sup.1H} NMR (C.sub.6D.sub.6, 75.4 MHz, 293 K): 166.3 (CN), 138.6 (1-C.sub.6H.sub.4), 138.5 (6-C.sub.6H.sub.4), 132.0 (2-C.sub.6H.sub.4), 129.0 (3-C.sub.6H.sub.4), 126.8 (4-C.sub.6H.sub.4), 125.6 (5-C.sub.6H.sub.4), 123.8 (CMeCMeCAr), 120.5 (CMeCMeCAr), 119.0 (CAr), 43.9 (TiMe), 39.2 (NMe.sub.2), 11.9 (CMeCMeCAr), 11.7 (CMeCMeCAr) ppm. IR (NaCl plates, Nujol mull, cm.sup.1): 1596 (e), 1570 (s), 1560, 918 (m), 817 (s), 774 (m), 757 (s), 714 (s), 678 (m), 643 (w). Anal. found (calcd. for C.sub.20H.sub.28N.sub.2Ti): C, 69.82 (69.77); H, 8.34 (8.20); N, 7.92 (8.14) %. EI-MS: m/z=329 (5%, [MMe].sup.+), 314 (40%, [M-2Me].sup.+), 270 (20%, [M-2MeNMe.sub.2].sup.+). Single crystals suitable for X-ray diffraction were grown from a pentane solution at room temperature.

Synthesis of C5Me4H-2-C6H4C(NiPr2)NH (Compound 4)

(20) ##STR00012##

(21) To a stirring THF (60 mL) solution of diisopropylamine (11.5 mL, 81 mmol) cooled to 7820 C. was added dropwise MeMgBr (27 mL, 3.0 M in Et.sub.2O, 81 mmol). The resulting white suspension was allowed to warm slowly to RT. Following 10 min stirring at RT, the suspension was cooled to 78 C. and a solution of C.sub.5Me.sub.4H-2-C.sub.6H.sub.4CN (3.02 g, 13.5 mmol) in THF (40 mL) was added dropwise. Following slow warming to RT, the solution had turned dark red-brown. The solution was then stirred at RT for a further 16 h after which time the solution had turned dark red. Toluene (100 mL) followed by water (200 mL) was added to quench the reaction, the aqueous phase was removed and the organic layer was dried over MgSO.sub.4. The solvent was removed in vacuo giving a viscous orange oil. The crude product was purified by silica gel column chromatography (5-10% n-hexanes in Et.sub.2O). Yield=2.22 g (51%).

Alternative Preparation of Compound 4

(22) To a stirring THF (50 mL) solution of HN.sup.iPr.sub.2 (5.5 mL, 39.2 mmol) was added dropwise MeMgCl (13.1 mL, 3.0 M in THF, 39.2 mmol). The solution was stirred for 5 h at 60 C. resulting in formation of a colourless precipitate. The suspension was then cooled to 78 C. and a THF (25 mL) solution of C.sub.5Me.sub.4H-2-C.sub.6H.sub.4C(H)NOMe (1.0 g, 3.92 mmol) was added dropwise. The solution was slowly warmed to RT and stirred for 3 days. The reaction was quenched by slow, dropwise addition of water (1 mL), after 1.5 h the orange suspension was filtered. The solids were washed with Et.sub.2O (1025 mL). The organic phase was then dried over anhydrous magnesium sulphate and the volatiles were removed in vacuo affording Compound 4 (0.95 g (75%)) as an orange oil.

(23) .sup.1H NMR (major isomer (70%)) (CDCl.sub.3, 299.9 MHz, 293 K): 7.34-7.08 (4H, series of overlapping m, Ar), 3.62 (1H, sept, N(CHMe.sub.2).sub.2, .sup.3J=6.5 Hz), 3.44 (1H, br q, CHMe, .sup.3J=7.5 Hz), 3.19 (1H, sept, N(CHMe.sub.2).sub.2, .sup.3J=6.5 Hz), 1.85 (3H, s, CMeCMeCMe), 1.83 (3H, s, CMeCMeCAr), 1.67 (3H, br s, CMeCMeCHMe), 1.08 (6H, d, N(CHMe.sub.2), .sup.3J=6.5 Hz), 0.87 (3H, d, CHMe, .sup.3J=7.5 Hz), 0.74 (6H, d, N(CHMe.sub.2), .sup.3J=6.5 Hz) ppm (NH not observed). .sup.13C-{.sup.1H} NMR (major isomer) (CDCl.sub.3, 75.4 MHz, 293 K): 158.8 CN(N.sup.iPr.sub.2), 141.6 (CMeCMeCHMe), 139.7 (CAr), 138.2 (1-C.sub.6H.sub.4 or 6-C.sub.6H.sub.4), 137.6 (CMeCMeCMe), 133.6 (CMeCMeCAr), 130.7 (Ar CH), 128.2 (6-C.sub.6H.sub.4 or 1-C.sub.6H.sub.4), 127.2 (Ar CH), 126.7 (Ar CH), 126.2 (Ar CH), 51.5 (N(CHMe.sub.2).sub.2), 51.4 (N(CHMe.sub.2).sub.2), 51.0 (CHMe), 15.3 (N(CHMe.sub.2).sub.2), 15.1 (CHMe), 14.2 (N(CHMe.sub.2).sub.2), 12.3 (CMeCMeCHMe), 12.1 (CMeCMeCMe), 11.3 (CMeCMeCAr) ppm. IR (thin film, cm.sup.1): 3389 (s, u(NH)), 2962 (s), 2855 (s), 2753 (m), 1953 (m), 1697 (s), 1621 (s), 1573 (s), 1447 (m), 1367 (m), 1260 (m), 1179 (w), 1026 (s), 921 (w), 802 (s), 761 (s), 733 (m), 699 (m), 680 (w). ESI.sup.+-HRMS: m/z=325.2638 (calcd. for [C.sub.22H.sub.33N.sub.2].sup.+ m/z=325.2638).

Synthesis of {5,1-C5Me4-2-C6H4C(NiPr2)N}TiCl2 (Compound 5)

(24) ##STR00013##

(25) To a stirring toluene (30 mL) solution of Ti(NMe.sub.2).sub.4 (1.60 mL, 6.90 mmol) was added dropwise a toluene (20 mL) solution of C.sub.5Me.sub.4H-2-C.sub.5H.sub.4C(N.sup.iPr.sub.2)NH (Compound 4) (2.22 g, 6.90 mmol). The solution immediately turned from orange to dark red and was stirred for a further 6 h at RT. The volatiles were then removed in vacuo and the solid extracted into toluene (40 mL). Trimethylsilyl chloride (1.90 mL, 15.2 mmol) was added dropwise and the solution was stirred for a further 16 h. The volatiles were again removed in vacuo and the dark red solid extracted into benzene (25 mL). The desired product crystallised as a red/orange solid from the concentrated benzene solution (15 mL) and, after washing thoroughly with pentane (420 mL), was isolated and dried in vacuo. Yield=1.84 g (61%). .sup.1H NMR (Toluene-d.sub.8, 299.9 MHz, 213 K): 7.15-7.00 (4H, series of overlapping m, Ar), 3.73 (1H, sept, CHMe.sub.2 cis to Ar, .sup.3J=6.0 Hz), 2.75 (1H, sept, CHMe.sub.2 trans to Ar, .sup.3J=6.3 Hz), 2.23 (6H, s, CMeCMeCAr), 1.97 (3H, s, CMeCMeCAr (closer to Ar)), 1.60 (6H, br s, two peaks overlapping: 3H, d, CHMe.sub.2 trans to Ar and 3H, s, CMeCMeCAr (further from Ar)), 1.41 (3H, d, CHMe.sub.2 trans to Ar, .sup.3J=5.9 Hz), 0.76 (3H, br d, CHMe.sub.2 cis to Ar, .sup.3J=6.0 Hz), 0.43 (3H, br d, CHMe.sub.2 cis to Ar, .sup.3J=6.0 Hz) ppm. .sup.13C-{.sup.1H} NMR (Toluene-d.sub.6, 75.4 MHz, 213 K): 167.6 (CN), 139.0 (1-C.sub.6H.sub.4), 138.1 (6-C.sub.6H.sub.4), 132.0 (Ar CH), 130.6 (Ar CH), 129.9 (Ar CH), 128.0 (MeCMeCAr), 127.2 (CMeCMeCAr), 126.6 (CMeCMeCAr (further from Ar)), 126.4 (CMeCMeCAr (closer to Ar)), 126.1 (Ar CH), 124.1 (CAr), 53.6 (CHMe.sub.2 cis to Ar), 48.2 (CHMe.sub.2 trans to Ar), 20.8 (CHMe.sub.2 cis to Ar), 20.3 (two peaks overlapping: CHMe.sub.2 cis to Ar and CHMe.sub.2 trans to Ar), 18.5 (CHMe.sub.2 trans to Ar), 14.7 (CMeCMeCAr (closer to Ar)), 13.0 (CMeCMeCAr (further from Ar)), 12.2 (CMeCMeCAr), 11.7 (CMeCMeCAr) ppm. IR (NaCl plates, Nujol mull, cm.sup.1): 1595 (w), 1569 (w), 1304 (s), 1261 (s), 1151 (m), 1083 (m), 1018 (s), 966 (w), 890 (m), 801 (m), 771 (m). Anal. found (calcd. for C.sub.22H.sub.30Cl.sub.2N.sub.2Ti.0.1 (C.sub.6H.sub.6)): C, 60.30 (60.45); H, 6.84 (6.87); N, 5.60 (6.24) %. EI-MS: m/z=440 (3%, [M].sup.+), 397 (100%, [M.sup.iPr].sup.+), 340 (70%, [MN.sup.iPr.sub.2].sup.+), 305 (30%, [MN.sup.iPr.sub.2Cl].sup.+), 222 (50%, [MTiCl.sub.2N.sup.iPr.sub.2].sup.+), 78 (100%, [Ph].sup.+). Single crystals suitable for X-ray diffraction were grown from a benzene solution at room temperature.

Synthesis of {5,1-C5Me4-2-C6H4C(NiPr2)N}TiMe2 (Compound 6)

(26) ##STR00014##

(27) To a stirring toluene (30 mL) solution of {.sup.5,.sup.1-C.sub.5Me.sub.4-2-C.sub.5H.sub.4C(N.sup.iPr.sub.2)N}TiCl.sub.2 (Compound 5) (0.66 g, 1.50 mmol) was added dropwise two equivalents of MeMgCl (1.00 mL, 3.0 M in THF, 3.00 mmol). Following stirring for 16 h, the volatiles were removed in vacuo and the resulting solid extracted into pentane (420 mL). The desired complex was recrystallised from a concentrated pentane solution (20 mL) at 30 C. as a yellow powder which was isolated and dried in vacuo. Yield=0.24 g (40%). .sup.1H NMR (C.sub.6D.sub.6, 299.9 MHz, 293 K): 7.34 (1H, d, 2-C.sub.6H.sub.4, .sup.3J=7.6 Hz), 7.14 (1H, d, 5-C.sub.6H.sub.4, .sup.3J=7.8 Hz), 7.08 (1H, dd, 3-C.sub.6H.sub.4, .sup.3J=7.5 Hz, 7.6 Hz), 6.93 (1H, dd, 4-C.sub.6H.sub.4, .sup.3J=7.5 Hz, 7.8 Hz), 3.47 (2H, br sept, CHMe.sub.2, .sup.3J=6.0 Hz), 2.20 (6H, s, CMeCMeCAr), 1.64 (6H, s, CMeCMeCAr), 1.28 (12H, br d, CHMe.sub.2, .sup.3J=6.0 Hz), 0.52 (6H, s, TiMe) ppm. .sup.13C-{.sup.1H} NMR (C.sub.6D.sub.6, 75.4 MHz, 293 K): 165.8 (CN), 141.6 (1-C.sub.6H.sub.4), 138.5 (6-C.sub.6H.sub.4), 132.8 (2-C.sub.6H.sub.4), 128.7 (3-C.sub.6H.sub.4), 125.8 (5-C.sub.1H.sub.4), 125.3 (4-C.sub.6H.sub.4), 123.6 (CMeCMeCAr), 120.4 (CAr), 119.4 (CMeCMeCAr), 50.0 (TiMe), 45.9 (CHMe.sub.2)), 21.1 (CHMe.sub.2), 12.5 (CMeCMeCAr), 11.7 (CMeCMeCAr) ppm. IR (NaCl plates, Nujol mull, cm.sup.1): 1570 (w), 1524 (s), 1313 (s), 1220 (w), 1024 (m), 889 (w), 783 (m), 758 (m), 674 (w). Anal. found (calcd. for C.sub.24H.sub.36N.sub.2Ti): C, 71.65 (71.99); H, 8.84 (9.06); N, 6.89 (7.00) %. EI-MS: m/z=385 (5%, [MMe].sup.+), 370 (40%, [M-2Me].sup.+), 270 (75%, [M-2MeN.sup.iPr.sub.2].sup.+). Single crystals suitable for X-ray diffraction were grown from benzene solution at room temperature.

Synthesis of C5Me4H-2-C6H4C(NCy2)NH (Compound 7)

(28) ##STR00015##

(29) To a stirring THF (100 mL) solution of dicyclohexylamine (26.9 mL, 135 mmol) cooled to 78 C. was added dropwise MeMgBr (45 mL, 3.0 M in Et.sub.2O, 135 mmol). The resulting yellow solution was allowed to warm slowly to RT. Following 10 min stirring at RT, the solution was cooled to 78 C. and a solution of C.sub.5Me.sub.4H-2-C.sub.6H.sub.4CN (5.02 g, 22.5 mmol) in THF (40 mL) was added dropwise. Following slow warming to RT, the solution had turned dark red-brown. The solution was then stirred at RT for a further 16 h after which time the solution had turned dark red. Water (400 mL) was added to quench the reaction, the aqueous phase was removed and the organic layer was dried over MgSO.sub.4. The volatiles were removed in vacuo affording a viscous orange oil. The crude product was purified by silica gel column chromatography (5-10% n-hexanes, 5% HN.sup.iPr, in Et.sub.2O). Yield=3.07 g (34%). .sup.1H NMR (major isomer (70%)) (CDCl.sub.3, 299.9 MHz, 293 K): 7.31-7.08 (4H, series of overlapping m, Ar), 5.78 (1H, s, NH), 3.46 (1H, qn, CHC.sub.5H.sub.10, .sup.3J=7.0 Hz), 3.44 (1H, br q, CHMe, .sup.3J=7.5 Hz), 2.99 (1H, br m, CHC.sub.5H.sub.10), 1.85 (3H, s, CMeCMeCMe), 1.82 (3H, s, CMeCMeCAr), 1.60 (3H, br s, CMeCMeCHMe), 1.74-0.91 (20H, series of overlapping m for CHC.sub.5H.sub.10), 0.86 (3H, d, CHMe, .sup.3J=7.5 Hz) ppm. .sup.13C-{.sup.1H} NMR (major isomer) (CDCl.sub.3, 75.4 MHz, 293 K): 168.3 CN(NCy.sub.2), 142.7 (CMeCMeCHMe), 141.6 (CAr), 138.2 (1-C.sub.6H.sub.4 or 6-C.sub.6H.sub.4), 133.3 (CMeCMeCMe), 131.1 (CMeCMeCAr), 128.6 (Ar CH), 128.2 (6-CH.sub.4 or 1-C.sub.6H.sub.4), 127.5 (Ar CH), 127.0 (Ar CH), 126.5 (Ar CH), 59.7 (CHC.sub.5H.sub.10), 51.2 (CHMe), 46.3 (CHC.sub.5H.sub.10), 28.1 (CHC.sub.5H.sub.10), 26.9 (CHC.sub.5H.sub.10), 26.8 (CHC.sub.5H.sub.10), 26.5 (CHC.sub.5H.sub.10), 26.3 (CHC.sub.5H.sub.10), 26.2 (CHC.sub.5H.sub.10), 25.6 (CHC.sub.5H.sub.10), 25.5 (CHC.sub.5H.sub.10), 22.8 (CHC.sub.5H.sub.10), 22.7 (CHC.sub.5H.sub.10), 15.4 (CHMe), 12.8 (CMeCMeCHMe), 12.0 (CMeCMeCMe), 11.2 (CMeCMeCAr) ppm. IR (thin film, cm.sup.1): 3311 (s, u(NH)), 3057 (m), 2926 (s), 2853 (s), 1702 (s), 1573 (s), 1484 (m), 1446 (s), 1379 (s), 1326 (m), 1273 (m), 1255 (m), 1194 (s), 1125 (s), 1042 (w), 991 (m), 920 (w), 894 (m), 841 (w), 812 (w), 760 (s), 716 (w), 972 (m), 602 (m). ESI.sup.+-HRMS: m/z=405.3250 (calcd. for [C.sub.29H.sub.41N.sub.2].sup.+ m/z=405.3264).

Synthesis of {5,1-C5Me4-2-C6H4C(NCy2)N}TiCl2 (Compound 8)

(30) ##STR00016##

(31) To a stirring toluene (30 mL) solution of Ti(NMe.sub.2).sub.4 (1.80 mL, 7.59 mmol) was added dropwise a toluene (20 mL) solution of C.sub.5Me.sub.4H-2-C.sub.6H.sub.4C(NCy.sub.2)NH (Compound 7) (3.07 g, 7.59 mmol). The solution immediately turned from orange to dark red and was stirred for a further 6 h at RT. The volatiles were then removed in vacuo and the solid extracted into toluene (40 mL). Trimethylsilyl chloride (2.60 mL, 20.4 mmol) was added dropwise and the solution was stirred for a further 16 h. The volatiles were again removed in vacuo and the dark red solid washed with pentane (320 mL) and subsequently extracted into hot toluene (60 mL). The desired product crystallized after storage for 16 h at 30 C. The crystals were washed with pentane (320 mL) and dried in vacuo. Yield=1.26 g (32%). .sup.1H NMR (CD.sub.2Cl.sub.2, 299.9 MHz, 293 K): 7.60-7.39 (4H, series of overlapping m, Ar), 3.92 (1H, br m, CHC.sub.5H.sub.10), 2.98 (1H, br m, CHC.sub.5H.sub.10), 2.16 (6H, s, CMeCMeCAr), 1.91-1.10 (20H, series of overlapping m for CHC.sub.5H.sub.10), 1.81 (6H, s, CMeCMeCAr) ppm. .sup.13C-{.sup.1H} NMR (CD.sub.2Cl.sub.2, 75.4 MHz, 293 K): 168.7 (CN), 138.9 (1-C.sub.6H.sub.4), 138.5 (6-C.sub.6H.sub.4), 132.6 (Ar CH), 130.5 (Ar CH), 129.3 (CMeCMeCAr), 128.5 (CMeCMeCAr), 126.8 (Ar CH), 126.3 (Ar CH), 125.3 (CAr), 63.2 (CHC.sub.5H.sub.10), 59.7 (CHC.sub.5H.sub.10), 32.5 (CHC.sub.5H.sub.10), 32.3 (CHC.sub.5H.sub.10), 28.9 (CHC.sub.5H.sub.10), 28.7 (CHC.sub.5H.sub.10), 26.7 (CHC.sub.5H.sub.10), 26.6 (CHC.sub.5H.sub.10), 26.5 (CHC.sub.5H.sub.10), 26.1 (CHC.sub.5H.sub.10), 25.9 (CHC.sub.5H.sub.10), 25.4 (CHC.sub.5H.sub.10), 13.6 (CMeCMeCAr), 12.2 (CMeCMeCAr) ppm. IR (NaCl plates, Nujol mull, cm.sup.1): 1569 (m), 1504 (s), 1332 (m), 1317 (s), 1260 (m), 1249 (w), 1160 (w), 1018 (m), 992 (s), 895 (m), 830 (s), 781 (m), 759 (s), 709 (w), 691 (m), 646 (w). Anal. found (calcd. for C.sub.28H.sub.38Cl.sub.2N.sub.2Ti): C, 64.67 (64.50); H, 7.35 (7.35); N, 5.15 (5.37) %. EI-MS: m/z=520 (3%, [M].sup.+), 437 (100%, [MCy].sup.+), 340 (60%, [MNCy.sub.2].sup.+), 305 (40%, [MClNCy.sub.2].sup.+). Single crystals suitable for X-ray diffraction were grown by slow cooling of a benzene solution from 70 C. to room temperature.

Synthesis of {5,1-C5Me4-2-C6H4C(NCy2)N}TiMe, (Compound 9)

(32) ##STR00017##

(33) To a stirring toluene (30 mL) solution of {.sub.5,.sup.1-C.sub.5Me.sub.4-2-C.sub.6H.sub.4C(NCy.sub.2)N}TiCl.sub.2 (Compound 8) (1.00 g, 1.92 mmol) was added dropwise two equivalents of MeLi (2.40 mL, 1.6 M in Et.sub.2O, 3.84 mmol). Following stirring for 3 h, the volatiles were removed in vacuo and the resulting solid extracted into n-hexanes (420 mL). The desired complex was recrystallised from a concentrated n-hexanes solution (30 mL) at 30 C. as a yellow powder which was isolated and dried in vacuo. Yield=0.34 g (37%). .sup.1H NMR (C.sub.6D.sub.6, 299.9 MHz, 293 K): 7.35 (1H, d, 2-C.sub.6H.sub.4, .sup.3J=7.6 Hz), 7.21 (1H, d, Ar, 5-C.sub.6H.sub.4, .sup.3J=7.8 Hz), 7.07 (1H, dd, 3-C.sub.6H.sub.4, .sup.3J=7.4 Hz, 7.6 Hz), 6.93 (1H, dd, 4-C.sub.5H.sub.4, .sup.3J=7.4 Hz, 7.8 Hz), 3.30 (2H, br m, CHC.sub.5H.sub.10), 2.21 (6H, s, CMeCMeCAr), 1.69 (6H, s, CMeCMeCAr), 1.65-0.85 (20H, series of overlapping m for CHC.sub.5H.sub.10), 0.53 (6H, s, TiMe) ppm. .sup.13C-{.sup.1H} NMR (C.sub.6D.sub.6, 75.4 MHz, 293 K): 166.0 (CN), 141.4 (1-C.sub.6H.sub.4), 138.6 (6-C.sub.6H.sub.4), 132.9 (2-C.sub.6H.sub.4), 128.7 (3-C.sub.6H.sub.4), 125.5 (5-C.sub.6H.sub.4), 125.2 (4-C.sub.6H.sub.4), 123.5 (CMeCMeCAr), 120.5 (CAr), 119.5 (CMeCMeCAr), 60.2 (br, CHC.sub.5H.sub.10), 46.2 (TiMe), 32.0 (CHC.sub.5H.sub.10), 31.4 (CHC.sub.5H.sub.10), 25.8 (CHC.sub.5H.sub.10), 23.1 (CHC.sub.5H.sub.10), 14.3 (CHC.sub.5H.sub.10), 12.7 (CMeCMeCAr), 11.8 (CMeCMeCAr) ppm. IR (NaCl plates, Nujol mull, cm.sup.1): 2360 (s), 2340 (m), 1304 (s), 1078 (m), 966 (m), 892 (w), 668 (s), 480 (s). Anal. found (calcd. for C.sub.30H.sub.44N.sub.2Ti): C, 74.92 (74.98); H, 9.52 (9.23); N, 5.57 (5.83) %. EI-MS m/z 465 (3%, [MMe].sup.+), 450 (25%, [M-2Me].sup.+), 270 (20%, [M-2MeNCy.sub.2].sup.+). Single crystals suitable for X-ray diffraction were grown from a benzene solution at room temperature.

(34) Part II: Batch EPDM Co-Polymerisations (General Procedure)

(35) 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+/3 C. 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.

(36) In an inert atmosphere of nitrogen, the reactor was filled with pentamethylheptanes (PMH) (950 mL), MAO-10T (Crompton, 10 wt % in toluene), BHT, 5-ethylidene-2-norbonene (ENB) (0.7 mL), 5-vinyl-2-norbonene (VNB) (0.7 mL) and dicyclopentadiene (DCPD) (0.7 mL) respectively. 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. (When TBF20 was used; the borate was added directly after the catalyst was added). 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).

(37) The experimental conditions and results are given in table 1.

(38) TABLE-US-00001 Metal- organic Residual Incor- Metal- compound Ti in porated organic MAO dosage Yield polymer C2 ENB VNB DCPD IV Mw Mz Example Compound (mol) (mol) (g) (ppm).sup.1 (wt %) (wt %) (wt %) (wt %) (dl/g) (kg/mol) (kg/mol) Mw/Mn 5.sup.3 6 450 0.25 5.9 2.0 40 0 0 0 3.1 300 560 2.5 6 6 500 0.50 2.0 12 39 1.6 0.9 0 2.8 280 490 2.2 7.sup.2 6 500 0.50 1.4 17 42 1.4 0 1.1 2.8 280 490 2.2 8.sup.3 9 500 0.50 9.8 2.5 39 0 0 0 1.9 210 360 2.2 9 9 500 0.50 4.7 5.1 38 1.5 1.0 0 2.2 205 360 2.6 Compar. 5 B 450 0.07 6.6 0.5 51 1.1 0.7 0 2.8 230 440 2.4 Compar. 6.sup.2 B 450 0.05 15 0.2 56 1.0 0 0.8 2.7 210 400 2.5 Compar. 7.sup.3 C 450 0.30 4.41 3.3 34 0 0 0 0.5 31 220 2.9 Compar. 9.sup.3 D 450 0.30 2.90 5.0 37 0 0 0 0.5 31 250 3.1 Compar. 10 C 450 0.50 3.18 7.5 33 2.0 1.2 0 0.5 28 130 4.3 Compar. 11 D 450 0.50 3.48 6.9 36 1.5 1.0 0 0.6 44 280 5.7 BHT/Al = 2 mol/mol; TBF20/Ti = 2 mol/mol; C3 feed = 400 NL/h; C2 feed = 200 NL/h; ENB feed = 0.7 ml; VNB feed = 0.7 ml; H2 feed = 0.35 NL/h T = 90 C.; P = 7 barg .sup.1Calculated value .sup.20.7 ml of DCPD in the feed of the 0.7 ml VNB .sup.3Ethylene-propylene copolymerization; no H2 added

(39) From the composition of the polymer given in Table 1, it can be concluded that the diene affinity of the catalysts 6 and 9 according to the invention is higher than the diene affinity of the known catalyst B.

RESULTS

(40) 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. the amount of catalyst was chosen to give a heat formation in this range. Even though the catalyst amount might be different the data can be used to establish certain results.

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

(42) The inventive compounds lead to higher Mw values than possible with R1=alkyl (see compounds C and D) known from EP1426379B1.