POLYMERISATION OF OLEFINS

Abstract

A process for the polymerisation of olefins is provided, which uses a Group IV transition metal catalyst.

Claims

1. A process for the polymerisation of at least one olefin, the process comprising the step of contacting the at least one olefin with a compound having a structure according to formula (I-A), (I-B) or (I-C) shown below: ##STR00021## wherein M is a Group IV transition metal, each X is independently selected from halo, hydrogen, a phosphonate, sulfonate or boronate group, (1-4C)dialkylamino, (1-6C)alkyl, (1-6C)alkoxy, aryl, and aryloxy, any of which may be optionally substituted one of more groups selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl, (1-6C)alkoxy, aryl and Si[(1-4C)alkyl].sub.3, R.sub.2 is absent or is selected from hydrogen, halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl, (1-6C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl and (1-6C)alkoxy, bond a is a carbon-nitrogen single bond (CN) or a carbon-nitrogen double bond (CN), with the proviso that when R.sub.2 is absent, bond a is a carbon-nitrogen double bond (CN), and when R.sub.2 is other than absent, bond a is a carbon-nitrogen single bond (CN), R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are each independently selected from hydrogen, halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl, (1-6C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl and (1-6C)alkoxy, R.sub.7 is selected from (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl, aryl, heteroaryl, carbocyclyl and heterocyclyl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl and (1-6C)alkoxy, R.sub.1 is a group having the formula (II) shown below: ##STR00022## wherein R.sub.a is selected from (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl, (1-6C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, L is a group [C(R.sub.x).sub.2].sub.n wherein each R.sub.x is independently selected from hydrogen, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl, (1-6C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl and aryl, and n is 0, 1, 2, 3 or 4.

2. The process of claim 1, wherein the compound has a structure according to formula (I-A) or (I-B).

3. The process of claim 1, wherein the compound has a structure according to formula (I-A).

4. The process of claim 1, wherein the compound has a structure according to formula (I-B).

5. The process of claim 1, wherein the compound has a structure according to formula (I-C).

6. The process of any preceding claim, wherein M is selected from titanium, zirconium and hafnium.

7. The process of any preceding claim, wherein M is selected from titanium and zirconium.

8. The process of any preceding claim, wherein M is titanium.

9. The process of any preceding claim, wherein each X is independently selected from halo, hydrogen, (1-6C)alkoxy, N(CH.sub.3).sub.2, N(CH.sub.2CH.sub.3).sub.2, and aryloxy, any of which may be optionally substituted one of more groups selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl, (1-6C)alkoxy, aryl and Si[(1-4C)alkyl].sub.3.

10. The process of any preceding claim, wherein each X is independently selected from halo, hydrogen, (1-6C)alkoxy, and aryloxy, any of which may be optionally substituted one of more groups selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl, (1-6C)alkoxy, aryl and Si[(1-4C)alkyl].sub.3.

11. The process of any one of claims 1 to 9, wherein each X is independently selected from halo, hydrogen, (1-6C)alkoxy, N(CH.sub.3).sub.2, N(CH.sub.2CH.sub.3).sub.2 and aryloxy, any of which may be optionally substituted one of more groups selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, (1-6C)alkoxy and aryl.

12. The process of claim 11, wherein each X is independently selected from halo, hydrogen, (1-6C)alkoxy, and aryloxy, any of which may be optionally substituted one of more groups selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, (1-6C)alkoxy and aryl.

13. The process of any one of claims 1 to 9, wherein each X is independently selected from halo, hydrogen, (1-4C)alkoxy, N(CH.sub.3).sub.2, N(CH.sub.2CH.sub.3).sub.2 and phenoxy, any of which may be optionally substituted one of more groups selected from halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl, (1-4C)alkoxy and phenyl.

14. The process of claim 13, wherein each X is independently selected from halo, hydrogen, (1-4C)alkoxy, and phenoxy, any of which may be optionally substituted one of more groups selected from halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl, (1-4C)alkoxy and phenyl.

15. The process of any preceding claim, wherein each X is independently selected from halo, hydrogen, and (1-4C)alkoxy, any of which may be optionally substituted one of more groups selected from halo, hydroxy, amino, (1-4C)alkyl and (1-4C)alkoxy.

16. The process of any preceding claim, wherein each X is independently selected from chloro, bromo and (1-4C)alkoxy.

17. The process of any preceding claim, wherein each X is independently (1-4C)alkoxy.

18. The process of any preceding claim, wherein each X is isopropoxy.

19. The process of any one of claims 1 to 9, wherein each X is independently N(CH.sub.3).sub.2 or N(CH.sub.2CH.sub.3).sub.2.

20. The process of any preceding claim, wherein R.sub.2 is absent or hydrogen.

21. The process of any preceding claim, wherein R.sub.2 is absent.

22. The process of any one or claims 1 to 20, wherein R.sub.2 is hydrogen.

23. The process of any preceding claim, wherein R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are each independently selected from hydrogen, halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl and (1-4C)alkoxy.

24. The process of any preceding claim, wherein R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are each independently selected from hydrogen, halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy.

25. The process of any preceding claim, wherein R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are each independently selected from hydrogen, halo, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo and (1-4C)alkyl.

26. The process of any preceding claim, wherein R.sub.3 is hydrogen.

27. The process of any preceding claim, wherein R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are hydrogen.

28. The process of any preceding claim, wherein R.sub.7 is selected from (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl and (1-6C)alkoxy.

29. The process of any preceding claim, wherein R.sub.7 is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy.

30. The process of any preceding claim, wherein R.sub.7 is selected from (1-4C)alkyl, (1-4C)haloalkyl, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-4C)alkyl and (1-4C)alkoxy.

31. The process of any preceding claim, wherein R.sub.7 is selected from (1-4C)alkyl and aryl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-4C)alkyl and (1-4C)alkoxy.

32. The process of any preceding claim, wherein R.sub.7 is selected from (1-2C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino and (1-4C)alkyl.

33. The process of any preceding claim, wherein R.sub.7 is selected from (1-2C)alkyl, which may be optionally substituted with one or more substituents selected from halo (e.g. fluoro).

34. The process of any preceding claim, wherein R.sub.7 is (1-2C)alkyl.

35. The process of any preceding claim, wherein R.sub.7 is methyl.

36. The process of any preceding claim, wherein R.sub.a is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl.

37. The process of any preceding claim, wherein R.sub.a is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy.

38. The process of any preceding claim, wherein R.sub.a is selected from (1-4C)alkyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy.

39. The process of any preceding claim, wherein R.sub.a is selected from aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy.

40. The process of any preceding claim, wherein R.sub.a is selected from phenyl, phenoxy, 5-7 membered heteroaryl, 5-7 membered heteroaryloxy, 5-12 membered carbocyclyl and 5-12 membered heterocyclyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-5C)alkyl, (1-5C)haloalkyl, phenyl, phenoxy, heteroaryl and heteroaryloxy.

41. The process of any preceding claim, wherein R.sub.a is selected from phenyl, 5-7 membered heteroaryl and 5-12 membered carbocyclyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-5C)alkyl, (1-5C)haloalkyl, phenyl, and heteroaryl.

42. The process of any preceding claim, wherein R.sub.a is selected from phenyl and 5-12 membered carbocyclyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-5C)alkyl, (1-5C)haloalkyl, phenyl, and heteroaryl.

43. The process of any preceding claim, wherein R.sub.a is selected from phenyl, cyclohexyl and adamantyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, (1-5C)alkyl, phenyl, and heteroaryl.

44. The process of any preceding claim, wherein each R.sub.x is independently selected from hydrogen, (1-6C)alkyl, (1-6C)alkoxy and aryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl and (1-6C)haloalkyl.

45. The process of any preceding claim, wherein each R.sub.x is independently selected from hydrogen, (1-4C)alkyl, (1-4C)alkoxy and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-6C)alkyl.

46. The process of any preceding claim, wherein each R.sub.x is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl.

47. The process of any preceding claim, wherein each R.sub.x is phenyl.

48. The process of any preceding claim, wherein n is 0, 1 or 2.

49. The process of any preceding claim, wherein n is 0 or 1.

50. The process of any preceding claim, wherein the compound is immobilized on a supporting substrate.

51. The process of claim 50, wherein the supporting substrate is a solid.

52. The process of claim 50 or 51, wherein the supporting substrate is selected from solid methyaluminoxane, silica, silica-supported methylaluminoxane, alumina, zeolite, layered double hydroxide and layered double hydroxide-supported methylaluminoxane.

53. The process of claim 50, 51 or 52, wherein the supporting substrate is solid methylaluminoxane.

54. The process of any preceding claim, wherein the at least one olefin is at least one (2-10C)alkene.

55. The process of any preceding claim, wherein the at least one olefin is at least one -olefin.

56. The process of any preceding claim, wherein the at least one olefin is ethene and optionally one or more other (3-10C)alkenes (e.g. 1-hexene, styrene and/or methyl methacrylate).

57. The process of any preceding claim, wherein the at least one olefin is ethene.

58. The process of any preceding claim, wherein the mole ratio of the compound of formula (I-A), (I-B) or (I-C) to the at least one olefin is 1:50 to 1:10,000.

59. The process of any preceding claim, wherein the mole ratio of the compound of formula (I-A), (I-B) or (I-C) to the at least one olefin is 1:100 to 1:1000.

60. The process of any preceding claim, wherein the mole ratio of the compound of formula (I-A), (I-B) or (I-C) to the at least one olefin is 1:150 to 1:300.

61. The process of any preceding claim, wherein the process is conducted in a solvent selected from toluene, hexane and heptane.

62. The process of any preceding claim, wherein the process is conducted for a period of 1 minute to 96 hours.

63. The process of any preceding claim, wherein the process is conducted for a period of 5 minute to 72 hours.

64. The process of any preceding claim, wherein the process is conducted at a pressure of 0.9 to 10 bar.

65. The process of any preceding claim, wherein the process is conducted at a pressure of 1.5 to 3 bar.

66. The process of any preceding claim, wherein the process is conducted at a temperature of 30 to 120 C.

67. The process of any preceding claim, wherein the process is conducted in the presence of an activator or co-catalyst.

68. The process of claim 67, wherein the activator or co-catalyst is one or more organoaluminium compounds.

69. The process of claim 68, wherein the one or more organoaluminium compounds are selected from methylaluminoxane, triisobutylaluminum and triethylaluminium.

Description

EXAMPLES

[0246] One or more examples of the invention will now be described, for the purpose of illustration only, with reference to the accompanying figures, in which:

[0247] FIG. 1 shows the .sup.1H NMR spectrum of HL.sub.1 in CDCl.sub.3 at 400 MHz

[0248] FIG. 2 shows the .sup.1H NMR spectrum of HL.sub.2 in CDCl.sub.3 at 400 MHz

[0249] FIG. 3 shows the .sup.1H NMR spectrum of HL.sub.3 in CDCl.sub.3 at 400 MHz

[0250] FIG. 4 shows the .sup.1H NMR spectrum of HL.sub.4 in CDCl.sub.3 at 400 MHz

[0251] FIG. 5 shows the .sup.1H NMR spectrum of HL.sub.5 in CDCl.sub.3 at 400 MHz

[0252] FIG. 6 shows the .sup.1H NMR spectrum of HL.sub.6 in CDCl.sub.3 at 400 MHz

[0253] FIG. 7 shows the .sup.1H NMR spectrum of HL.sub.7 in CDCl.sub.3 at 400 MHz

[0254] FIG. 8 shows the .sup.1H NMR spectrum of HL.sub.8 in CDCl.sub.3 at 400 MHz

[0255] FIG. 9 shows the .sup.1H NMR spectrum of (Li).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 400 MHz

[0256] FIG. 10 shows the .sup.13C{.sup.1H} NMR spectrum of (Li).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 125 MHz

[0257] FIG. 11 shows the ORTEP representation of (Li).sub.2Ti(O.sup.iPr).sub.2. Ellipsoids drawn at 50% probability, hydrogens and disorder omitted for clarity. Green=Titanium, Blue=Nitrogen, Scarlet=Oxygen, Gray=Carbon, Lime=Fluorine.

[0258] FIG. 12 shows the .sup.1H NMR spectrum of (L.sub.2).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 400 MHz

[0259] FIG. 13 shows the ORTEP representation of (L.sub.2).sub.2Ti(O.sup.iPr).sub.2. Ellipsoids drawn at 50% probability, hydrogens and disorder omitted for clarity. Green=Titanium, Blue=Nitrogen, Scarlet=Oxygen, Gray=Carbon.

[0260] FIG. 14 shows the .sup.1H NMR spectrum of (L.sub.3).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 400 MHz

[0261] FIG. 15 shows the .sup.13C{.sup.1H} NMR spectrum of (L.sub.3).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 125 MHz

[0262] FIG. 16 shows the ORTEP representation of (L.sub.3).sub.2Ti(O.sup.iPr).sub.2. Ellipsoids drawn at 50% probability, hydrogens and disorder omitted for clarity. Green=Titanium, Blue=Nitrogen, Scarlet=Oxygen, Gray=Carbon.

[0263] FIG. 17 shows the .sup.1H NMR spectrum of (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 400 MHz.

[0264] FIG. 18 shows the .sup.13C{.sup.1H} NMR spectrum of (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 125 MHz.

[0265] FIG. 19 shows the ORTEP representation of (L.sub.4).sub.2Ti(O.sup.iPr).sub.2. Ellipsoids drawn at 50% probability, hydrogens, disorder, and isopropyls omitted for clarity. Green=Titanium, Blue=Nitrogen, Scarlet=Oxygen, Gray=Carbon

[0266] FIG. 20 shows the ORTEP representation of (L.sub.5).sub.2Ti(O.sup.iPr).sub.2. Ellipsoids drawn at 50% probability, hydrogens and disorder omitted for clarity. Green=Titanium, Blue=Nitrogen, Scarlet=Oxygen, Gray=Carbon.

[0267] FIG. 21 shows the .sup.1H NMR spectrum of (L.sub.6).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 400 MHz

[0268] FIG. 22 shows the .sup.13C{.sup.1H} NMR spectrum of (L.sub.6).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 125 MHz

[0269] FIG. 23 shows the ORTEP representation of (L.sub.6).sub.2Ti(O.sup.iPr).sub.2. Ellipsoids drawn at 50% probability, hydrogens and disorder omitted for clarity. Green=Titanium, Blue=Nitrogen, Scarlet=Oxygen, Gray=Carbon.

[0270] FIG. 24 shows the .sup.1H NMR spectrum of (L.sub.7).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 400 MHz

[0271] FIG. 25 shows the .sup.13C{.sup.1H} NMR spectrum of (L.sub.7).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 125 MHz

[0272] FIG. 26 shows the ORTEP representation of (L.sub.7).sub.2Ti(O.sup.iPr).sub.2. Ellipsoids drawn at 50% probability, hydrogens and disorder omitted for clarity. Green=Titanium, Blue=Nitrogen, Scarlet=Oxygen, Gray=Carbon.

[0273] FIG. 27 shows the .sup.1H NMR spectrum of (L.sub.8).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 400 MHz

[0274] FIG. 28 shows the .sup.13C{.sup.1H} NMR spectrum of (L.sub.8).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 125 MHz

[0275] FIG. 29 shows the ORTEP representation of (L.sub.8).sub.2Ti(O.sup.iPr).sub.2. Ellipsoids drawn at 50% probability, hydrogens and disorder omitted for clarity. Green=Titanium, Blue=Nitrogen, Scarlet=Oxygen, Gray=Carbon.

[0276] FIG. 30 shows the .sup.1H NMR spectrum of (L.sub.2).sub.2ZrCl.sub.2 in CDCl.sub.3 at 400 MHz.

[0277] FIG. 31 shows the .sup.1H NMR spectrum of (L.sub.3).sub.2ZrCl.sub.2 in CDCl.sub.3 at 400 MHz.

[0278] FIG. 32 shows comparative .sup.1H NMR spectra of (Li).sub.2Ti(O.sup.iPr).sub.2 and HL.sub.1, in CDCl.sub.3, 400 MHz.

[0279] FIG. 33 shows comparative .sup.1H NMR spectra of (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 and HL.sub.4, in CDCl.sub.3, 400 MHz

[0280] FIG. 34 shows comparative .sup.1H NMR spectra of (L.sub.7).sub.2Ti(O.sup.iPr).sub.2 and HL.sub.7, in CDCl.sub.3, 400 MHz

[0281] FIG. 35 shows variable temperature NMR of the imine region of (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 in d.sup.6-THF (500 MHz).

[0282] FIG. 36 shows variable high temperature .sup.1H NMR (500 MHz) of (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 in d.sup.2-tetrachloroethane

[0283] FIG. 37 shows .sup.1H NMR of (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 in d.sup.2-tetrachloroethane before heating (Top) and after heating for 24 h at 100 C. (bottom).

[0284] FIG. 38 shows variable low temperature .sup.1H NMR (500 MHz) of (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 in d.sup.8-THF

[0285] FIG. 39 shows .sup.1H NMR of (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 in d.sup.8-THF before heating (top) and after heating for 5 h at 70 C. (bottom).

[0286] FIG. 40 shows the .sup.1H NMR spectrum of HL.sub.4 in CDCl.sub.3, 400 MHz.

[0287] FIG. 41 shows the .sup.13C{.sup.1H} NMR spectrum of HL.sub.4 in CDCl.sub.3, 400 MHz.

[0288] FIG. 42 shows the .sup.1H NMR spectrum of HL.sub.5 in CDCl.sub.3, 400 MHz.

[0289] FIG. 43 shows the .sup.13C{.sup.1H} NMR spectrum of HL.sub.5 in CDCl.sub.3, 400 MHz.

[0290] FIG. 44 shows the .sup.1H NMR spectrum of HL.sub.6 in CDCl.sub.3, 400 MHz.

[0291] FIG. 45 shows the .sup.13C{.sup.1H} NMR spectrum of HL.sub.6 in CDCl.sub.3, 400 MHz.

[0292] FIG. 46 shows the .sup.1H NMR spectrum of HL.sub.7 in CDCl.sub.3, 500 MHz.

[0293] FIG. 47 shows the .sup.1H NMR spectrum of HL.sub.4.sup.F in CDCl.sub.3, 400 MHz.

[0294] FIG. 48 shows the .sup.1H NMR spectrum of [(LF.sub.4).sub.2Ti(O.sup.iPr).sub.2] in CDCl.sub.3, 400 MHz, as well as the .sup.19F{.sup.1H} NMR spectrum comparing HL.sup.F.sub.4 (58.1 ppm) and [(L.sup.F.sub.4).sub.2Ti(O.sup.iPr).sub.2] (58.4) 400 MHz in CDCl.sub.3.

[0295] FIG. 49 shows the .sup.1H NMR spectrum of (L.sub.4).sub.2Ti(OEt).sub.2 in CDCl.sub.3 at 298 K.

[0296] FIG. 50 shows the .sup.13C{.sup.1H} NMR spectrum of (L.sub.4).sub.2Ti(OEt).sub.2 in CDCl.sub.3 at 298 K.

[0297] FIG. 51 shows the .sup.1H NMR spectrum of (L.sub.4).sub.2Ti(O.sup.iPO.sub.2 in CDCl.sub.3 at 298 K.

[0298] FIG. 52 shows the .sup.13C{.sup.1H} NMR spectrum of (L.sub.4).sub.2Ti(O.sup.iPO.sub.2 in CDCl.sub.3 at 298 K.

[0299] FIG. 53 shows the .sup.1H NMR spectrum of (L.sub.5).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 298 K.

[0300] FIG. 54 shows the .sup.13C{.sup.1H} NMR spectrum of (L.sub.5).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 298 K.

[0301] FIG. 55 shows the .sup.1H NMR spectrum of (L.sub.6).sub.2Ti(O.sup.iPO.sub.2 in CDCl.sub.3 at 298 K.

[0302] FIG. 56 shows the .sup.13C{.sup.1H} NMR spectrum of (L.sub.6).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 298 K.

[0303] FIG. 57 shows the .sup.1H NMR spectrum of (L.sub.7).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 298 K. 400 MHz.

[0304] FIG. 58 shows X-ray crystal structures of (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 (left) and (L.sub.7).sub.2Ti(O.sup.iPr).sub.2 (right) showing Type C coordination.

[0305] FIG. 59 shows low temperature .sup.1H NMR spectrum of complex (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 in d.sup.8-THF (top) and high temperature .sup.1H NMR spectrum of complex (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 (bottom) in C.sub.6D.sub.6.

[0306] FIG. 60 shows Low temperature .sup.1H NMR of complex (L.sub.5).sub.2Ti(O.sup.iPO.sub.2 (shown in its conjectured structure) in THF-d.sup.8 (* THF or hexane) (top) and high temperature .sup.1H NMR of complex (L.sub.5).sub.2Ti(O.sup.iPr).sub.2 in C.sub.6D.sub.6 (bottom).

[0307] FIG. 61 shows Low temperature .sup.1H NMR spectrum of complex (L.sub.6).sub.2Ti(O.sup.iPO.sub.2 in d.sup.6-THF (top) and high temperature .sup.1H NMR of complex (L.sub.6).sub.2Ti(O.sup.iPr).sub.2 in C.sub.6D.sub.6 (bottom).

[0308] FIG. 62 shows X-ray crystal structures of (L.sub.4).sub.2Ti(OEt).sub.2 (left), (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 (middle), and (L.sub.4).sub.2Ti(NMe.sub.2).sub.2 (right) showing the variability of coordination based on initiator.

[0309] FIG. 63 shows a) ethylene polymerization activity of catalysts (L.sub.4-6).sub.2Ti(O.sup.iPO.sub.2 in the slurry and solution phase. b) SEM of polyethylene derived from (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 immobilized on sMAO. Magnification 1000. c) SEM of polyethylene derived from (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 initiated with MAO. Magnification 1000.

[0310] FIG. 64 shows (left) the ethylene homopolymerization activity of (L.sub.4-6).sub.2Ti(O.sup.iPr).sub.2 and (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 at various temperatures and pressures; (right) the ethylene/1-hexene copolymerization activity of (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 and (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 at various temperatures.

MATERIALS AND METHODS

[0311] All metal complexes were synthesized under anhydrous conditions, using MBraun gloveboxes and standard Schlenk techniques. Solvents and reagents were obtained from Sigma Aldrich or Strem and were used as received unless stated otherwise. THF and toluene were dried by refluxing over sodium and benzophenone and stored under nitrogen. All dry solvents were stored under nitrogen and degassed by several freeze-pump-thaw cycles. NMR spectra were recorded using a Bruker AV 400 or 500 MHz spectrometer. Correlation between proton and carbon atoms were obtained by COSY, HSQC, and HMBC spectroscopic methods and subsequently assigned. Elemental analysis was carried out by Mr. Stephen Boyer of the London Metropolitan University.

[0312] Crystals suitable for single crystal x-ray diffraction were grown either through slow evaporation of hexanes into THF or through low temperature crystallization in concentrated THF at 30 C. Samples were isolated in a glovebox under a pool of fluorinated oil and mounted on MiTeGen MicroMounts. The crystal was then cooled to 150 K with an Oxford Cryosystems Cryostream nitrogen cooling device. Data collection was carried out with an Oxford Diffraction Supernova diffractometer using Cu K (=1.5417 ) or Mo K (=0.7107 ) radiation. The resulting raw data was processed using CrysAlisPro. Structures were solved by SHELXT and Full-matrix least-squares refinements based on F.sup.2 were performed in SHELXL-14.sup.1, as incorporated in the WinGX package..sup.2 For each methyl group, the hydrogen atoms were added at calculated positions using a riding model with U(H)=1.5 Ueq (bonded carbon atom). The rest of the hydrogen atoms were included in the model at calculated positions using a riding model with U(H)=1.2 Ueq (bonded atom). Neutral atom scattering factors were used and include terms for anomalous dispersion..sup.3

Part A

Example 1Ligand Synthesis

[0313] A variety of ligands, HL.sub.1-HL.sub.8, were prepared according to the general synthesis depicted in Scheme 1 shown below:

##STR00015##

Synthesis of HL.SUB.1

[0314] o-Vanillin (5 g, 32.9 mmol) was added to a round bottom flask and dissolved in ethanol (60 mL). 2,3,4,5,6-pentafluoroaniline (6.02 g, 32.9 mmol) was added into the stirring solution along with several drops of formic acid. This reaction mixture was refluxed for 72 hours resulting in a bright orange precipitate and a pale yellow solution. Precipitate was filtered, washed with ethanol (20 mL) and pentane (320 mL) and dried under vacuum. Crude product was then washed with hot ethanol (30 mL) and dried. Yield: 3.67 g (35%) .sup.1H NMR (400 MHz, CDCl.sub.3) (ppm): 12.58 (s, 1H), 8.85 (s, 1H), 7.05 (m, 2H), 6.93 (t, 1H), 3.94 (s, 3H).

[0315] FIG. 1 shows the .sup.1H NMR spectrum of HL.sub.1 in CDCl.sub.3 at 400 MHz.

Synthesis of HL.SUB.2

[0316] o-Vanillin (2.75 g, 18.0 mmol) was added to a round bottom flask and dissolved in ethanol (30 mL). Cyclohexylamine (1.79 g, 18.0 mmol) was syringed into the stirring solution along with several drops of formic acid. Reaction mixture was refluxed for 18 hours resulting in an orange solution. Volatiles were removed under vacuum yielding a viscus yellow oil. The oil was placed in a 30 C. freezer to solidify into a soft yellow solid. Yield: 3.85 g (91%) .sup.1H NMR (400 MHz, CDCl.sub.3) (ppm): 8.29 (s, 1H), 6.88-6.82 (m, 2H), 6.73 (t, 1H), 3.87 (s, 3H), 3.28 (m, 1H), 1.81 (m, 4H), 1.62-1.32 (m, 6H).

[0317] FIG. 2 shows the .sup.1H NMR spectrum of HL.sub.2 in CDCl.sub.3 at 400 MHz.

Synthesis of HL.SUB.3

[0318] o-Vanillin (3 g, 19.7 mmol) was added to a round bottom flask and dissolved in ethanol (30 mL). 2,6-dimethylaniline (2.34 g, 19.7 mmol) was syringed into the stirring solution along with several drops of formic acid. Reaction mixture was refluxed for 18 hours resulting in a yellow solution. Upon removal of several mL of ethanol under vacuum yellow solid precipitated from solution. This solid was filtered and washed with pentane (320 mL). The resulting dark yellow powder was dried to remove residual solvent. Yield: 3.57 g (71%) .sup.1H NMR (400 MHz, CDCl.sub.3) (ppm): 13.5 (bs, 1H), 8.35 (s, 1H), 7.12 (m, 2H), 7.04 (m, 2H), 6.97 (m, 1H), 6.91 (t, 1H), 3.96 (s, 3H), 2.21 (s, 6H).

[0319] FIG. 3 shows the .sup.1H NMR spectrum of HL.sub.3 in CDCl.sub.3 at 400 MHz.

Synthesis of HL.SUB.4

[0320] o-Vanillin (3 g, 19.7 mmol) was added to a round bottom flask and dissolved in ethanol (30 mL). 2,6-diisopropylaniline (3.5 g, 19.7 mmol) was syringed into the stirring solution along with several drops of formic acid. Reaction mixture was refluxed for 18 hours resulting in an orange solution. Upon cooling to room temperature copious amounts of large orange crystals formed. These crystals were filtered, washed with pentane (320 mL) and dried under vacuum. Yield: 5.0 g (82%) .sup.1H NMR (400 MHz, CDCl.sub.3) (ppm): 13.5 (bs, 1H), 8.34 (s, 1H), 7.21 (m, 3H), 7.21-7.02 (m, 2H), 7.0 (t, 1H), 3.98 (s, 4H), 3.03, (sep, 2H), 1.20 (d, 12H).

[0321] FIG. 4 shows the .sup.1H NMR spectrum of HL.sub.4 in CDCl.sub.3 at 400 MHz.

Synthesis of HL.SUB.5

[0322] o-Vanillin (5 g, 32.9 mmol) was added to a round bottom flask and dissolved in ethanol (25 mL). 2-aminobiphenyl (5.56 g, 32.9 mmol) was added to the stirring solution along with several drops of formic acid. The reaction mixture was refluxed for 24 hours resulting in a deep red solution. Volatiles were removed under vacuum. Yield: 8.06 g (81%). .sup.1H NMR (400 MHz, CDCl.sub.3) (ppm): 12.9 (1H, bs), 8.60 (s, 1H), 7.43-7.36 (m, 8H), 7.22 (d, 1H), 6.96 (m, 2H), 6.86 (t, 1H), 3.88 (s, 3H).

[0323] FIG. 5 shows the .sup.1H NMR spectrum of HL.sub.5 in CDCl.sub.3 at 400 MHz.

Synthesis of HL.SUB.6

[0324] o-Vanillin (3 g, 19.7 mmol) was added to a round bottom flask and dissolved in ethanol (30 mL). Adamantan-1-amine (2.98 g, 19.7 mmol) was then added to the stirring solution along with several drops of formic acid. Reaction mixture was refluxed for 20 hours resulting in an orange solution. Volatiles were removed under vacuum yielding an orange solid which was washed with pentane (20 mL3) Yield: 3.67 g, (65%) .sup.1H NMR (400 MHz, CDCl.sub.3) (ppm): 15.16 (bs, 1H), 8.25 (s, 1H), 6.85 (m, 2H), 6.69 (t, 1 h), 3.88 (s, 3H), 2.19 (m, 3H), 1.85 (d, 6H), 1.73 (m, 6H).

[0325] FIG. 6 shows the .sup.1H NMR spectrum of HL.sub.6 in CDCl.sub.3 at 400 MHz.

Synthesis of HL.SUB.7

[0326] o-Vanillin (1.5 g, 9.86 mmol) was added to a round bottom flask and dissolved in ethanol (30 mL). 2,4,6-tritertbutylaniline (2.58 g, 9.86 mmol) was added into the stirring solution along with several drops of formic acid. Reaction mixture was refluxed for 18 hours resulting in an orange solution. Volatiles were removed under vacuum to yield a yellow solid which was recrystallized from hot ethanol (30 mL). The pure yellow crystalline product was washed with cold pentane (20 mL3) and dried under vacuum. Yield: 2.8 g (71%) .sup.1H NMR (400 MHz, CDCl.sub.3) (ppm): 13.8 (s, 1H), 8.24 (s, 1H), 7.41 (s, 2H), 7.03 (m, 1H), 6.91 (m, 2H), 3.97 (s, 3H), 1.35 (s, 9H), 1.34 (s, 18H).

[0327] FIG. 7 shows the .sup.1H NMR spectrum of HL.sub.7 in CDCl.sub.3 at 400 MHz.

Synthesis of HL.SUB.8

[0328] o-Vanillin (1.5 g, 9.86 mmol) was added to a round bottom flask and dissolved in ethanol (30 mL). tritylamine (2.56 g, 9.86 mmol) was added into the stirring solution along with several drops of formic acid. This reaction mixture was refluxed for 24 hours resulting in a bright yellow precipitate and a pale yellow solution. Precipitate was filtered, washed with ethanol (30 mL) and pentane (320 mL) and dried under vacuum. Yield: 3.65 g (94%) .sup.1H NMR (400 MHz, CDCl.sub.3) (ppm): 14.8 (s, 1H), 7.97 (s, 1H), 7.35-7.23 (m, 15H), 6.98 (dd, 1H), 6.82 (t, 1H), 6.78 (m, 1H), 3.97 (s, 3H).

[0329] FIG. 8 shows the .sup.1H NMR spectrum of HL.sub.8 in CDCl.sub.3 at 400 MHz.

Example 2Complex Synthesis

[0330] Using ligands HL.sub.1-HL.sub.8 prepared in Example 1, a variety of complexes, (Li).sub.2Ti(O.sup.iPr).sub.2-(L.sub.8).sub.2Ti(O.sup.iPr).sub.2, were prepared according to the general synthesis depicted in Scheme 2 shown below:

##STR00016##

[0331] The o-vanillin derived ligands were found to possess two separate modes of coordination to the metal: 6-membered N,O coordination, and 5-membered O,O coordination. These two coordination modes were found to be independent of one another, thus the eight catalysts synthesized each exhibit one of three basic types of coordination chemistries found to be possible in these systems. Type A: N,O:N,O coordination, Type B: N,O:O,O coordination, Type C: O,O:O,O coordination. Within each type there are also additional isomers that are theoretically possible. Upon increasing steric bulk, coordination around the metal centre rearranges from: Type A-I to Type A-II, then to Type B followed by Type C. (Scheme 3).

##STR00017##

Synthesis of (Li).sub.2Ti(O.sup.iPr).sub.2

[0332] HL.sub.1 (0.50 g, 1.58 mmol) and Ti(O.sup.iPr).sub.4 (0.224 g, 0.79 mmol) were dissolved separately in toluene (7 mL and 3 mL, respectively), and cooled to 30 C. in a glovebox freezer. The two solutions were then mixed and allowed to stir for 18 hours. Volatiles were removed in vacuo yielding a bright orange solid. Yield: 316 mg (50%) MALDI-TOF MS (m/z): 739.64 (calc. for [M.sup.+-O.sup.iPr=739.077]) .sup.1H NMR (400 MHz, CDCl.sub.3) (ppm): 8.23 (bs, 2H), 7.16 (bm, 4H), 6.93 (t, 2H), 4.88 (m, 2H), 3.82 (s, 6H), 1.17 (d, 12H). .sup.13C{.sup.1H} (125 MHz, CDCl.sub.3) (ppm): 171.4, 156.4, 149.5, 141.7, 139.3, 137.3, 136.4, 127.7, 126.2, 121.1, 117.3, 80.7, 56.3, 25.1 C.sub.34H.sub.28F.sub.10N.sub.2O.sub.6Ti (798.45 g/mol) Calculated: C, 51.15; H, 3.53; N, 3.51%. Found: C, 51.03; H, 3.39; N, 3.66%.

[0333] FIG. 9 shows the .sup.1H NMR spectrum of (Li).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 400 MHz.

[0334] FIG. 10 shows the .sup.13C{.sup.1H} NMR spectrum of (Li).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 125 MHz.

[0335] FIG. 11 shows the ORTEP representation of (Li).sub.2Ti(O.sup.iPr).sub.2. (Li).sub.2Ti(O.sup.iPr).sub.2 crystallize in the centrosymmetric space group P-1 and adopt Type A-I coordination, with imine nitrogens in a cis arrangement. Due to the low steric pressure exerted around the titanium metal centre by R.sub.1=C.sub.6F.sub.5 this complex prefers the coordination mode typically seen in salicylaldehyde derivatives. The coordination is reinforced by the electron deficient C.sub.6F.sub.5 substituent -stacking with the adjacent Ph-OMe substituent, with an average difference between rings of 3.10 .

Synthesis of (L.sub.2).sub.2Ti(O.sup.iPr).sub.2

[0336] HL.sub.2 (0.30 g, 1.29 mmol) and Ti(O.sup.iPr).sub.4 (0.183 g, 0.643 mmol) were dissolved separately in toluene (15 mL and 5 mL, respectively), and cooled to 30 C. in a glovebox freezer. The two solutions were then mixed and allowed to stir for 24 hours turning from yellow to light orange. Volatiles were removed in vacuo and hexane (30 mL) was added to the resulting orange-yellow wax. Crude mixture was recrystallized from a minimum of THF in a 30 C. freezer. Crude Yield: 332 mg (82%) MALDI-TOF MS (m/z): 571.3003 (calc. for [M.sup.+-O.sup.iPr=571.2651]) .sup.1H NMR (400 MHz, CDCl.sub.3) (ppm): 8.10 (bs, 2H), 6.87 (m, 2H), 6.81 (m, 2H), 6.67 (t, 2H), 3.86 (s, 6H), 2.07 (m, 2H), 1.85-0.88 (m, 30H), 0.36 (m, 2H). C.sub.34H.sub.50N.sub.2O.sub.6Ti (630.65 g/mol) Calculated: C, 64.75; H, 7.99; N, 4.44%. Found: C, 64.90; H, 8.05; N, 4.32%.

[0337] FIG. 12 shows the .sup.1H NMR spectrum of (L.sub.2).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 400 MHz.

[0338] FIG. 13 shows the ORTEP representation of (L.sub.2).sub.2Ti(O.sup.iPr).sub.2. (L.sub.2).sub.2Ti(O.sup.iPr).sub.2 crystallize in the centrosymmetric space group P-1 and adopt Type A-I coordination, with imine nitrogens in a cis arrangement. Due to the low steric pressure exerted around the titanium metal centre by R.sub.1=Cy this complex prefers the coordination mode typically seen in salicylaldehyde derivatives.

Synthesis of (L.sub.3).sub.2Ti(O.sup.iPr)

[0339] HL.sub.3 (0.246 g, 0.964 mmol) and Ti(O.sup.iPr).sub.4 (0.137 g, 0.482 mmol) were dissolved separately in toluene (15 mL and 5 mL, respectively), and cooled to 30 C. in a glovebox freezer. The two solutions were then mixed and allowed to stir for 24 hours. Volatiles were removed in vacuo and hexane (10 mL) was added to the resulting orange-yellow wax. This hexane was removed under vacuum to provide the final complex as a bright orange powder. Yield: 327 mg (99%). MALDI-TOF MS (m/z): 615.3101 (calc. for [M.sup.+-O.sup.iPr=615.2338]) .sup.1H NMR (400 MHz, CDCl.sub.3) (ppm): 8.18 (s, 2H), 7.3 (m, 1H)*, 6.91-6.86 (m, 9H), 6.70 (t, 2H), 4.82 (m, 2H), 4.00 (s, 6H), 2.14 (s, 12H), 1.11 (d, 12H) .sup.13C{.sup.1H} (125 MHz, CDCl.sub.3) (ppm): 156.2, 151.6, 149.5, 129.0, 128.7, 128.2, 127.6, 124.0, 121.9, 116.6, 80.1, 56.8, 25.4, 18.5 C.sub.38H.sub.46N.sub.2O.sub.6Ti (674.28 g/mol) Calculated: C, 67.65; H, 6.87; N, 4.15%. Found: C, 67.42; H, 6.89; N, 4.22%.

[0340] FIG. 14 shows the .sup.1H NMR spectrum of (L.sub.3).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 400 MHz

[0341] FIG. 15 shows the .sup.13C{.sup.1H} NMR spectrum of (L.sub.3).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 125 MHz.

[0342] FIG. 16 shows the ORTEP representation of (L.sub.3).sub.2Ti(O.sup.iPr).sub.2. Upon increasing steric hindrance to form (L.sub.3).sub.2Ti(O.sup.iPr).sub.2 a rearrangement is observed from Type A-I to Type A-II where imine nitrogens prefer a trans geometry. In this arrangement, steric pressure is relieved by creating space between R groups while still maintaining O,N:O,N coordination. As a result of this rearrangement, the TiN bond distances shorten and TiO distances elongate by 0.08 compared to (L.sub.2).sub.2Ti(O.sup.iPr).sub.2.

Synthesis of (L.sub.4).sub.2Ti(O.sup.iPr)

[0343] HL.sub.4 (0.30 g, 0.946 mmol) and Ti(O.sup.iPr).sub.4 (0.137 g, 0.482 mmol) were dissolved separately in toluene (15 mL and 5 mL, respectively), and cooled to 30 C. in a glovebox freezer. The two solutions were then mixed and allowed to stir for 24 hours. Volatiles were removed in vacuo and hexane (10 mL) was added to the resulting orange-yellow wax. This hexane was removed under vacuum to provide the final complex as a bright orange powder. Yield: 176 mg (46%) MALDI-TOF MS (m/z): 727.5702 (calc. for [M.sup.+-O.sup.iPr=727.3590]) .sup.1H NMR (400 MHz, CDCl.sub.3) (ppm): 8.59 (s, 2H), 7.67 (bs, 2H), 7.15 (m, 6H), 6.91 (d, 2H), 6.80 (t, 2H), 4.76 (m, 2H), 3.97 (s, 6H), 3.10 (bs, 4H), 1.19-1.15 (d, 38H) .sup.13C{.sup.1H} (125 MHz, CDCl.sub.3) (ppm): 159.9, 155.7, 150.0, 149.6, 138.3, 122.9, 121.9, 120.9, 117.3, 112.9, 80.6, 56.9, 27.8, 25.5, 23.7. C.sub.46H.sub.62N.sub.2O.sub.6Ti (786.9 g/mol): Calculated: C, 70.22; H, 7.94; N, 3.56%. Found: C, 70.17; H, 8.02; N, 3.56%.

[0344] FIG. 17 shows the .sup.1H NMR spectrum of (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 400 MHz.

[0345] FIG. 18 shows the .sup.13C{.sup.1H} NMR spectrum of (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 125 MHz.

[0346] FIG. 19 shows the ORTEP representation of (L.sub.4).sub.2Ti(O.sup.iPr).sub.2. (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 crystallizes in the chiral orthorhombic space group Pna2.sub.1 and adopts Type B coordination with one nitrogen trans to O.sup.iPr and one detached, in favour of OO coordination through the o-methoxy group. Due to the formation of a five-membered ring, the O(1)-TiO(2) bite angle is far more acute, at 72.92(8), than the O(3)-TiN(2) bite angle, which is similar to that seen in (L.sub.2).sub.2Ti(O.sup.iPr).sub.2, at 80.72(9). Additionally, TiO.sup.iPr distances are significantly shorter than in Type A by ca. 0.05 , and the bound imine moiety is 0.02 shorter than the unbound imine, which is expected.

Synthesis of (L.sub.5).sub.2Ti(O.sup.iPr)

[0347] HL.sub.5 (2 g, 6.60 mmol) and Ti(O.sup.iPr).sub.4 (0.937 g, 3.30 mmol) were dissolved separately in toluene (15 mL and 5 mL, respectively), and cooled to 30 C. in a glovebox freezer. The two solutions were then mixed and allowed to stir for 24 hours. Volatiles were removed in vacuo yielding an amber solid. Crude mixture was recrystallized by layering hexanes and THF. Yield: 2.28 g (89%). MALDI-TOF MS (m/z): 712.2714 (calc. for [M.sup.+-O.sup.iPr]=711.2338) .sup.1H NMR (400 MHz, CDCl.sub.3) (ppm): 8.36 (bs, 2H), 7.23 (m, 18H), 6.78 (bm, 2H), 6.60 (m, 2H), 4.87 (bm, 2H), 3.71 (s, 6H), 1.17 (m, 12H).

[0348] FIG. 20 shows the ORTEP representation of (L.sub.5).sub.2Ti(O.sup.iPr).sub.2. (L.sub.5).sub.2Ti(O.sup.iPr).sub.2 crystallizes in the centrosymmetric space group P2/n and adopts Type B coordination with one nitrogen trans to O.sup.iPr and one detached, in favour of OO coordination through the o-methoxy group. Due to the formation of a five-membered ring, the O(1)-TiO(2) bite angle is far more acute, at 72.92(8), than the O(3)-TiN(2) bite angle, which is similar to that seen in (L.sub.2).sub.2Ti(O.sup.iPr).sub.2, at 80.72(9). Additionally, TiO.sup.iPr distances are significantly shorter than in Type A by ca. 0.05 , and the bound imine moiety is 0.02 shorter than the unbound imine, which is expected.

Synthesis of (L.sub.6).sub.2Ti(O.sup.iPr)

[0349] HL.sub.6 (1.193 g, 3.03 mmol) and Ti(O.sup.iPr).sub.4 (0.429 g, 1.51 mmol) were dissolved separately in toluene (15 mL and 5 mL, respectively), and cooled to 30 C. in a glovebox freezer. The two solutions were then mixed and allowed to stir for 24 hours. Volatiles were removed in vacuo yielding a light yellow powder. Crude mixture was recrystallized by layering hexanes and THF. Yield: 1.29 g (90%) MALDI-TOF MS (m/z): 675.9662 (calc. for [M.sup.+-O.sup.iPr]=675.3277) .sup.1H NMR (400 MHz, CDCl.sub.3) (ppm): 8.77 (s, 2H), 7.54 (dd, 2H), 6.72 (m, 4H), 4.90 (m, 2), 3.77 (s, 6H), 2.16 (s, 6H). 1.85 (s, 12H), 1.73 (m, 12H), 1.33 (d, 12H). .sup.13C{.sup.1H} (125 MHz, CDCl.sub.3) (ppm): 154.1, 152.1, 149.3, 123.0, 120.1, 117.5, 111.1, 80.3, 57.9, 57.0, 43.4, 36.7, 29.8, 25.5.

[0350] FIG. 21 shows the .sup.1H NMR spectrum of (L.sub.6).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 400 MHz.

[0351] FIG. 22 shows the .sup.13C{.sup.1H} NMR spectrum of (L.sub.6).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 125 MHz.

[0352] FIG. 23 shows the ORTEP representation of (L.sub.6).sub.2Ti(O.sup.iPr).sub.2. (L.sub.6).sub.2Ti(O.sup.iPr).sub.2 crystallizes in a centrosymmetric space group and adopts Type C coordination, where steric bulk forces O,O chelation of both ligands. (L.sub.6).sub.2Ti(O.sup.iPr).sub.2 shows OTiO bite angles similar to those found in (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 at 73.67(5) [O(1)-TiO(2)] and 73.99(5) [O(3)-TiO(4)]. O.sup.iPr moieties arrange trans to the neutral OMe groups and TiO.sup.iPr distances are shorter than those found Type A and B complexes. (Table 1) Both Imine CN bonds are ca. 1.27 as expected.

Synthesis of (L.sub.7).sub.2Ti(O.sup.iPr)

[0353] HL.sub.7 (0.40 g, 1.01 mmol) and Ti(O.sup.iPr).sub.4 (0.144 g, 0.51 mmol) were dissolved separately in toluene (7 mL and 3 mL, respectively), and cooled to 30 C. in a glovebox freezer. The two solutions were then mixed and allowed to stir for 18 hours. Volatiles were removed in vacuo yielding an orange solid. Yield: 176 mg (46%) MALDI-TOF MS (m/z): 896.6176 (calc. for [M.sup.+-O.sup.iPr]=895.5468) .sup.1H NMR (400 MHz, CDCl.sub.3) (ppm): 8.71 (s, 2H), 7.82 (m, 2H), 7.39 (s, 4H), 6.84 (m, 4H), 4.60 (m, 2H), 3.82 (s, 6H), 1.37 (s, 36H), 1.35 (s, 18H), 1.11 (d, 12H). .sup.13C{.sup.1H} (125 MHz, CDCl.sub.3) (ppm): 157.8, 155.3, 151.4, 149.9, 143.6, 138.4, 121.7, 120.7, 117.7, 111.7, 80.7, 56.9, 36.0, 34.8, 31.7 31.5, 25.5. C.sub.58H.sub.86N.sub.2O.sub.6Ti (955.20 g/mol) Calculated: C, 72.93; H, 9.08; N, 2.93%. Found: C, 72.81; H, 9.17; N, 3.12%.

[0354] FIG. 24 shows the .sup.1H NMR spectrum of (L.sub.7).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 400 MHz.

[0355] FIG. 25 shows the .sup.13C{.sup.1H} NMR spectrum of (L.sub.7).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 125 MHz.

[0356] FIG. 26 shows the ORTEP representation of (L.sub.7).sub.2Ti(O.sup.iPr).sub.2. (L.sub.7).sub.2Ti(O.sup.iPr).sub.2 crystallizes in a centrosymmetric space group and adopts Type C coordination, where steric bulk forces O,O chelation of both ligands. O.sup.iPr moieties arrange trans to the neutral OMe groups and TiO.sup.iPr distances are shorter than those found Type A and B complexes. (Table 1) Both Imine CN bonds are ca. 1.27 as expected.

Synthesis of (L.sub.8).sub.2Ti(O.sup.iPr)

[0357] HL.sub.8 (2.04 g, 5.18 mmol) was suspended in toluene (20 mL) and THF (5 mL) and Ti(O.sup.iPr).sub.4 (0.736 g, 2.59 mmol) dissolved in toluene (5 mL) was added dropwise. The yellow suspension cleared after several minutes of stirring and allowed to react for 24 hours. Volatiles were removed in vacuo yielding a light yellow solid. Yield: 2.32 (94%) MALDI-TOF MS (m/z): 891.3367 (calc. for [M.sup.+-O.sup.iPr]=891.3277) .sup.1H NMR (400 MHz, CDCl.sub.3) (ppm): 8.40 (s, 2H), 7.91 (dd, 2H), 7.32-7.23 (m, 30H), 6.72 (m, 4H), 4.59 (m, 2H), 3.64 (s, 6H), 1.06 (d, 12H). .sup.13C{.sup.1H} (125 MHz, CDCl.sub.3) (ppm): 156.2, 154.8, 149.3, 146.4, 129.9, 127.6, 126.6, 125.3, 122.5, 120.3, 117.4, 111.1, 80.3, 78.4, 56.9, 25.5. C.sub.60H.sub.58N.sub.2O.sub.6Ti (951.00 g/mol) Calculated: C, 75.78; H, 6.15; N, 2.95%. Found: C, 75.88; H, 6.24; N, 3.03%.

[0358] FIG. 27 shows the .sup.1H NMR spectrum of (L.sub.8).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 400 MHz.

[0359] FIG. 28 shows the .sup.13C{.sup.1H} NMR spectrum of (L.sub.8).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 125 MHz.

[0360] FIG. 29 shows the ORTEP representation of (L.sub.8).sub.2Ti(O.sup.iPr).sub.2. (L.sub.8).sub.2Ti(O.sup.iPr).sub.2 crystallizes in a centrosymmetric space group and adopts Type C coordination, where steric bulk forces O,O chelation of both ligands. O.sup.iPr moieties arrange trans to the neutral OMe groups and TiO.sup.iPr distances are shorter than those found Type A and B complexes. (Table 1) Both Imine CN bonds are ca. 1.27 as expected.

[0361] Using ligands HL.sub.2 and HL.sub.3 prepared in Example 1, complexes (L.sub.2).sub.2ZrCl.sub.2 and (L.sub.3).sub.2ZrCl.sub.2 were prepared according to the general synthesis depicted in Scheme 4 shown below

##STR00018##

Synthesis of (L.sub.2).sub.2ZrCl.sub.2

[0362] HL.sub.2 (0.40 g, 1.71 mmol) and K[N(SiMe.sub.3).sub.2] (0.342 g, 1.71 mmol) were dissolved separately in THF (5 mL and 3 mL, respectively). The K[N(SiMe.sub.3).sub.2] solution was then added dropwise to the stirring solution of ligand and allowed to react for 24 hours. ZrCl.sub.4(THF).sub.2 (0.323 g, 0.857 mmol) was dissolved in THF (5 mL) and added to the deprotonated ligand. After stirring for 24 hours the resulting cloudy yellow solution was centrifuged and the solution was decanted. Volatiles were removed in vacuo and hexane (10 mL) was added to the resulting yellow wax. This hexane was removed under vacuum to provide the final complex as a light powder. MALDI-TOF MS (m/z): 589.1416 (calc. for [M.sup.+-Cl=589.1411]) .sup.1H NMR (400 MHz, CDCl.sub.3) (ppm): 8.18 (s, 2H), 7.06 (m, 2H), 6.89 (t, 2H), 6.87 (m, 2H), 4.16 (m, 2H), 3.98 (s, 6H), 3.74 (m, 4H, THF), 1.85 (m, 4H, THF), 1.59-1.07 (bm, 20H). Calculated: C, 53.66; H, 5.79; N, 4.47%. C, 53.78; H, 5.80; N, 4.31%.

[0363] FIG. 30 shows the .sup.1H NMR spectrum of (L.sub.2).sub.2ZrCl.sub.2 in CDCl.sub.3 at 400 MHz.

Synthesis of (L.sub.3).sub.2ZrCl.sub.2

[0364] HL.sub.3 (0.246 g, 0.964 mmol) and K[N(SiMe.sub.3).sub.2] (0.192 g, 0.964 mmol) were dissolved separately in THF (5 mL and 3 mL, respectively). The K[N(SiMe.sub.3).sub.2] solution was then added dropwise to the stirring solution of ligand and allowed to react for 24 hours. ZrCl.sub.4(THF).sub.2 (0.182 g, 0.482 mmol) was dissolved in THF (5 mL) and added to the deprotonated ligand. After stirring for 24 hours the resulting cloudy yellow solution was centrifuged and the solution was decanted. Volatiles were removed in vacuo and hexane (10 mL) was added to the resulting yellow wax. This hexane was removed under vacuum to provide a light powder, which could be recrystallized by layering of hexanes and THF. Yield: 0.282 mg, 87.3%. MALDI-TOF MS (m/z): 633.1627 (calc. for [M.sup.+-Cl=633.1098]) .sup.1H NMR (400 MHz, CDCl.sub.3) (ppm): 8.33 (s, 2H), 7.09 (m, 6H), 7.06 (d, 2H), 7.0 (d, 2H), 6.90 (t, 2H), 3.78 (s, 6H), 2.45 (s, 12H).

[0365] FIG. 31 shows the .sup.1H NMR spectrum of (L.sub.3).sub.2ZrCl.sub.2 in CDCl.sub.3 at 400 MHz.

Example 3Crystallographic Studies

[0366] Table 1 below provides a summary of the TO distances in complexes (L.sub.1).sub.2Ti(O.sup.iPr).sub.2-(L.sub.8).sub.2Ti(O.sup.iPr).sub.2.

TABLE-US-00001 TABLE 1 Summary of TO distances in complexes (L.sub.1).sub.2Ti(O.sup.iPr).sub.2-(L.sub.8).sub.2Ti(O.sup.iPr).sub.2 Compound TiO.sup.iPr(1) Dist. () TiO.sup.iPr(2) Dist. () Coordination Type (L.sub.1).sub.2Ti(O.sup.iPr).sub.2 1.847(2) 1.834(2) A-I (L.sub.2).sub.2Ti(O.sup.iPr).sub.2* 1.77 1.81 A-I (L.sub.3).sub.2Ti(O.sup.iPr).sub.2 1.795(1) 1.803(1) A-II (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 1.77 1.786(2) B (L.sub.5).sub.2Ti(O.sup.iPr).sub.2 1.787(1) 1.800(1) B (L.sub.6).sub.2Ti(O.sup.iPr).sub.2 1.760(2) 1.785(2) C (L.sub.5).sub.2Ti(O.sup.iPr).sub.2 1.758(2) 1.776(2) C (L.sub.8).sub.2Ti(O.sup.iPr).sub.2 1.774(2) 1.780(2) C *An average is given between the two enantiomers in the asymmetric unit

[0367] Table 2 below provides select crystallographic details for (L.sub.1).sub.2Ti(O.sup.iPr).sub.2-(L.sub.4).sub.2Ti(O.sup.iPr).sub.2.

TABLE-US-00002 TABLE 2 Select crystallographic details for (L.sub.1).sub.2Ti(O.sup.iPr).sub.2-(L.sub.4).sub.2Ti(O.sup.iPr).sub.2 Compound (L.sub.1).sub.2Ti(O.sup.iPr).sub.2 (L.sub.2).sub.2Ti(O.sup.iPr).sub.2 (L.sub.3).sub.2Ti(O.sup.iPr).sub.2 (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 Chemical formula C.sub.34H.sub.28F.sub.10N.sub.2O.sub.6Ti C.sub.37H.sub.57N.sub.2O.sub.6Ti C.sub.38H.sub.45N.sub.2O.sub.6Ti C.sub.46H.sub.62N.sub.2O.sub.6Ti Formula weight 798.48 673.74 674.67 786.87 Temp (K.) 150(2) 150(2) 150(2) 150(2) Space group Triclinic, P-1 Triclinic, P-1 Triclinic, P-1 Orthorhombic, Pna2.sub.1 a () 13.7054(3) 10.9569(3) 10,2329(3) 23,3761(6) b () 14.1810(4) 13.4552(4) 10.4196(2) 13.2107(3) c () 19.1110(5) 14.3513(4) 19.4022(5) 14.8217(4) () 10.121(2) 103.976(3) 79.916(2) () 102.985(2) 105.967(2) 79.672(2) () 91.205(2) 109.032(3) 66,375(2) V (A.sup.3) 3379.78(16) 1790.69(10) 1756.99(8) 4577.2(2) Z 4 2 2 4 D.sub.calcd (Mg/m.sup.3) 1.570 1.250 1.275 1.142 Crystal size (mm) 0.27 0.20 0.08 0.25 0.20 0.06 0.25 0.25 0.15 0.25 0.15 0.08 Theta range for data collection () 3.655 to 76.329 3.732 to 76.089 4.663 to 76.178 3.843 to 76.405 (mm.sup.1) (Cu, K) 3,093 (Cu, K) 2.394 (Cu, K) 2.449 (Cu, K) 1.944 Reflections collected 51454 26538 38003 51906 Unique reflections 13998 [R.sub.int = 0.0293] 7376 [R.sub.int = 0.0365] 7295 [R.sub.int = 0.0276] 8674 [R.sub.int = 0.0605] Data Completeness to [] 100.0% [67.684] 100.0% [67.684] 100.0% [67.684] 100.0% [67.684] Data/restraints/parameters 13998/12/979 7376/0/422 7295/0/434 8674/45/533 R1.sup.a (%) (all data) 3.00 (3.50) 4.44 (5.22) 3.04 (3.21) 4.20 (4.60) wR.sub.2.sup.b (%)(all data) 7.75 (8.07) 12.55 (13.38) 8.41 (8.55) 10.70 (11.36) Goodness-of-fit on F.sup.2 1.025 1.062 1.047 1.025 Largest diff peak and hole (e .sup.3) 0.334 and 0.380 1.187 and 0.411 0.254 and 0.379 0.396 and 0.409 .sup.aR1 = F.sub.o| |F.sub.c/|F.sub.o| 100 .sup.bwR2 = [w(F.sub.o.sup.2 F.sub.c.sup.2).sup.2/(w|F.sub.o|.sup.2).sup.2].sup.1/2 100

[0368] Table 3 below select crystallographic details for (L.sub.5).sub.2Ti(O.sup.iPr).sub.2-(L.sub.8).sub.2Ti(O.sup.iPr).sub.2,

TABLE-US-00003 TABLE 3 Select crystallographic details for (L.sub.5).sub.2Ti(O.sup.iPr).sub.2-(L.sub.8).sub.2Ti(O.sup.iPr).sub.2 Compound (L.sub.5).sub.2Ti(O.sup.iPr).sub.2 (L.sub.6).sub.2Ti(O.sup.iPr).sub.2 (L.sub.7).sub.2Ti(O.sup.iPr).sub.2 (L.sub.8).sub.2Ti(O.sup.iPr).sub.2 Chemical formula C.sub.46H.sub.46N.sub.2O.sub.6Ti C.sub.42H.sub.58N.sub.2O.sub.6Ti C.sub.66H.sub.102N.sub.2O.sub.6Ti C.sub.63H.sub.65N.sub.2O.sub.6Ti Formula weight 770.75 734.80 1099.39 994.07 Temp (K.) 150( ) 150(2) 150(2) 150(2) Space group Monoclinic, P2.sub.1/n Monoclinic, P2.sub.1/c Monoclinic, P2.sub.1/c Triclinic, P-1 a () 16.0712(4) 22.6717(4) 19,6212(3) 9.3703(5) b () 9.9873(2) 14.4902(2) 17.3312(3) 16.9578(10) c () 25.2051(5) 12.0146(2) 19.3123(3) 18.9044(15) () 67.887(7) () 94.390(2) 91.2620(2) 95.4930(10) 86.252(5) () 75.730(5) V (A.sup.3) 4033.75(15) 3946.05(11) 6537.16(18) 2695.8(3) Z 4 4 4 2 D.sub.calcd (Mg/m.sup.3) 1.269 1.237 1.117 1.225 Crystal size (mm) 0.30 0.15 0.08 0.25 0.25 0.18 0.25 0.22 0.15 0.25 0.20 0.06 Theta range for data collection () 3.517 to 76.264 3.620 to 76.238 3.434 to 76.282 3.307 to 30.439 (mm.sup.1) (Cu, K) 2.205 (Cu, K) 2.218 (Cu, K) 1.510 (Mo, K) 0.212 Reflections collected 25780 36803 50743 27281 Unique reflections 8359 [R.sub.int = 0.0293] 8213 [R.sub.int = 0.0305] 13570 [R.sub.int = 0.0336] 13947 [R.sub.int = 0.0600] Data Completeness to [] 100.0% [67.684] 100.0% [67.684] 100.0% [67.684] 99.7% [25.000] Data/restraints/parameters 8359/0/502 8213/26/496 13570/167/846 13947/96/734 R1.sup.a (%) (all data) 3.53 (4.41) 4.58 (5.03) 4.85 (6.08) 7.33 (16.83) wR.sub.2.sup.b (%)(all data) 8.84 (9.48) 12.53 (12.99) 13.59 (14.69) 11.65 (14.90) Goodness-of-fit on F.sup.2 1.020 1.028 1.039 1.003 Largest diff peak and hole (e .sup.3) 0.259 and 0.334 0.733 and 0.476 0.454 and 0.524 0.324 and 0.396 .sup.aR1 = F.sub.o| |F.sub.c/|F.sub.o| 100 .sup.bwR2 = [w(F.sub.o.sup.2 F.sub.c.sup.2).sup.2/(w|F.sub.o|.sup.2).sup.2].sup.1/2 100

Example 4NMR Studies

[0369] Evidence of different isomers in solution can be seen by following the .sup.1H NMR spectra of each type. For (Li).sub.2Ti(O.sup.iPr).sub.2, which has Type A-I coordination, the imine CH resonance shifts up field by 0.67 ppm, relative to the parent ligand, and broadens significantly. (FIG. 32) (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 which adopts Type B coordination shows a single CH imine peak shifted 0.25 ppm downfield from the parent ligand, along with a slight broadening. (FIG. 33) Broadening is likely due to the rapid conversion between A and A enantiomers, along with fluxionality between the two asymmetrically bound ligands, vida infra. This rapid conversion has been seen previously in similar systems and can be frozen out by variable temperature NMR. Broadening can also be seen in the aryl .sup.iPr resonance at 3 ppm which suggests restricted rotation of these groups in solution. (L.sub.6-L.sub.8).sub.2Ti(O.sup.iPr).sub.2 adopt the third conformation, Type C, where both ligands are OO chelated, and they all display the same gross features in their .sup.1H NMR. In each case the imine CH resonance shifts significantly down field by ca. 0.5 ppm, while the OMe resonance shifts up field from the parent ligand. (FIG. 34)

Example 5Variable Temperature NMR

[0370] To better understand the nature of intermediate case of Type B catalysts, variable temperature NMR experiments were undertaken on (L.sub.4).sub.2Ti(O.sup.iPr).sub.2. As Type B coordination shows both N,O and O,O chelation, but only shows a single imine resonance, it was necessary to confirm that the asymmetry observed in the solid state structure remains in solution. (FIG. 35) Upon cooling (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 from room temperature to 80 C. the imine resonance at 8.6 ppm broadened and split into two peaks at 8.75 and 8.3 ppm. These two peaks correlate to the individual imine resonance on the O,N and O,O bound ligands. Additionally, the ppm value of the O,N imine resonance correlates closely with that seen in Type A complexes, 8.3 ppm, while the ppm value of the O,O resonance correlates to that seen in Type C complexes, 8.7 ppm. This indicates that the Type B coordination is retained in solution, and at room temperature signals are averaged due to dynamic exchange between ligands.

[0371] Upon heating (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 in d.sup.2-1,1,2,2-tetrachloroethane (TCE) incrementally from room temperature to 100 C., peaks sharpened slightly but did not shift (FIG. 36). Additionally, after being held at this temperature for 24 hours, the .sup.1H NMR of (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 showed no discernible change. There was also no change in the .sup.1H NMR after heating at 70 C. in d.sup.8-THF for five hours. This resilience at high temperature indicates that the molecule retains its structure under reaction conditions in both coordinating and non-coordinating solvent.

Example 6Catalyst Immobilisation

[0372] In a glovebox, sMAO (40.2 wt. % Al, 200 mg) and the desired catalyst (1.4910.sup.5 mmol) were added to a Schlenk flask. Toluene (40 mL) was then added and the slurry was heated at 60 C. for one hour with occasional stirring by hand. The suspension was allowed to settle for several hours at room temperature and the toluene was decanted by cannula. Finally, the resulting powder was dried under high vacuum for several hours to yield the final immobilized catalysts as pale yellow powder.

Example 7Polymerisation Studies

Ethylene Polymerisation

[0373] The standard conditions for carrying out the ethylene polymerisation process were as follows: In a glovebox, the immobilized catalyst (10 mg) was weighed into a thick walled ampule, along with triisobutylaluminum (TIBA, 150 mg), and hexane (50 mL). The ampule was then cycled on to a Schlenk line and the N.sub.2 atmosphere was partially removed under vacuum. The slurry was heated to the desired temperature and stirred vigorously prior to the addition of ethylene at 2 bar. After the desired time had elapsed, the ampule was removed from heat and ethylene was removed from the system under vacuum and replaced with N.sub.2. The resulting polymer was filtered, washed several times with pentane, and dried.

[0374] The polymerisation results are presented in Table 4 below:

TABLE-US-00004 TABLE 4 Ethylene polymerisation using selected (L.sub.x).sub.2Ti(O.sup.iPr).sub.2catalysts Temp Yield Coordination Entry Catalyst .sup.a ( C.) (mg) Activity.sup.b Type 1 (L.sub.5).sub.2Ti(O.sup.iPr).sub.2 80 24 64 B 2 (L.sub.8).sub.2Ti(O.sup.iPr).sub.2 80 47 127 C 3 (L.sub.8).sub.2Ti(O.sup.iPr).sub.2* 80 53 143 C 4 (L.sub.8).sub.2Ti(O.sup.iPr).sub.2 50 35 94 C .sup.a200:1 Al:Ti, sMAO, 10 mg supported catalyst, 150 mg TIBA, 50 mL hexane, 2 bar ethylene, 30 m .sup.bCalculated as (kg PE/mol catalyst time) *Duplicate run.

[0375] The results presented in Table 4 illustrate that the compounds of formula (I-A), (I-B) and (I-C) are effective in the polymerisation of olefins such as ethylene.

Part B

Example 8Ligand Synthesis

Amine Ligands

[0376] Following the formation of imine ligands previously described (L.sub.1-8) a reduction with excess NaBH.sub.4 could be performed to yield amine ligands (La). These ligands were characterized through .sup.1H and .sup.13C{.sup.1H} NMR.

##STR00019##

Synthesis of HL.SUB.4.

[0377] 2 equivalents of NaBH.sub.4 (0.49 g, 12.84 mmol) were slowly added to HL.sub.4 (2.00 g, 6.42 mmol) dissolved in ethanol (20 mL), and the solution was stirred for 2 hours, until it turned from yellow to colourless. Water (10 mL) was added dropwise to the flask at 0 C. causing a white precipitate to form. Concentrated HCl was added dropwise until a neutral pH was obtained. The reaction was left without stirring for an hour, then the solid was filtered, washed with cold water, and dried in a vacuum oven at 40 C. Isolated Yield: 1.91 g, 6.08 mmol, 95%. .sup.1H NMR (400 MHz, CDCl.sub.3) (ppm): 9.10 (s, 1H), 7.16 (s, 3H), 6.88-6.87 (d, 1H), 6.83 (t, 1H), 6.77-6.75 (d, 1H), 4.13 (s, 2H), 3.93 (s, 3H), 3.62 (bs, 1H), 3.35 (septet, 2H), 1.29-1.27 (d, 12H). .sup.13C{.sup.1H} NMR (125 MHz, CDCl.sub.3) (ppm): 148.0, 146.2, 143.1, 141.3, 125.4, 124.0, 123.9, 121.0, 119.5, 110.9, 56.1, 54.4, 28.1, 24.5.

[0378] FIG. 40 shows the .sup.1H NMR spectrum of HL.sub.4 in CDCl.sub.3, 400 MHz.

[0379] FIG. 41 shows the .sup.13C{.sup.1H} NMR spectrum of HL.sub.4 in CDCl.sub.3, 400 MHz.

Synthesis of HL.SUB.5.

[0380] 4 equivalents of NaBH.sub.4 (0.50 g, 13.19 mmol) were slowly added to HL.sub.5 (1.00 g, 3.30 mmol) which was partially dissolved in ethanol (20 mL), and the reaction was stirred for 3 hours, until the solution turned colourless. Water (40 mL) was added slowly to the flask at 0 C., and was left without stirring overnight, producing a small amount of off-white aggregated solid. The liquid was decanted off and recrystallised from ethanol to give a solid which was washed with pentane and dried under vacuum. Isolated Yield: 0.71 g, 2.32 mmol, 71%..sup.1H NMR (400 MHz, CDCl.sub.3) (ppm): 7.47-7.43 (m, 4H), 7.39-7.34 (m, 1H), 7.24-7.20 (td, 1H), 7.13-7.11 (dd, 1H), 6.87-6.79 (m, 5H), 6.38 (s, 1H), 4.44 (bs, 1H), 4.39-4.38 (m, 2H), 3.89 (s, 3H). .sup.13C{.sup.1H} NMR (125 MHz, CDCl.sub.3) (ppm): 146.7, 144.9, 144.0, 139.4, 130.2, 129.4, 128.9, 128.7, 128.5, 127.3, 124.5, 120.7, 119.5, 117.7, 111.6, 109.8, 56.0, 44.1.

[0381] FIG. 42 shows the .sup.1H NMR spectrum of HL.sub.5 in CDCl.sub.3, 400 MHz.

[0382] FIG. 43 shows the .sup.13C{.sup.1H} NMR spectrum of HL.sub.5 in CDCl.sub.3, 400 MHz.

Synthesis of HL.SUB.6.

[0383] 2 equivalents of NaBH.sub.4 (0.66 g, 17.52 mmol) were slowly added to HL.sub.6 (2.50 g, 8.76 mmol) dissolved in ethanol (30 mL), and the reaction was stirred for 2 hours, until the solution turned colourless, and a white precipitate appeared. Water (20 mL) was added dropwise to the flask at 0 C. without stirring. The solid formed was filtered, washed with cold water and dried under vacuum. Isolated Yield: 2.20 g, 7.66 mmol, 87%..sup.1H NMR (400 MHz, CDCl.sub.3) (ppm): 6.79-6.77 (m, 1H), 6.72 (t, 1H), 6.60-6.59 (m, 1H), 3.99 (s, 2H), 3.86 (s, 3H), 2.10 (bs, 3H), 1.72-1.60 (m, 12H). .sup.13C{.sup.1H} NMR (125 MHz, CDCl.sub.3) (ppm): 148.4, 147.9, 124.0, 119.9, 118.3, 110.6, 55.9, 51.3, 43.9, 42.1, 36.5, 29.4.

[0384] FIG. 44 shows the .sup.1H NMR spectrum of HL.sub.6 in CDCl.sub.3, 400 MHz.

[0385] FIG. 45 shows the .sup.13C{.sup.1H} NMR spectrum of HL.sub.6 in CDCl.sub.3, 400 MHz.

Synthesis of HL.SUB.7.

[0386] 12 equivalents of NaBH.sub.4 (1.15 g, 37.83 mmol) were added to HL.sub.7 (1 g, 2.5 mmol) dissolved in ethanol (30 mL), over the course of 8 hours, until the solution turned colourless. The next day water (60 mL) was added to the flask at 0 C. without stirring. The solid formed was filtered, washed with cold water and dried under vacuum. Isolated Yield: 0.937 g, 2.36 mmol, 95%..sup.1H NMR (500 MHz, CDCl.sub.3) (ppm): 7.97 (s, 1H), 7.34 (s, 2H), 6.90 (m, 1H), 6.84 (d, 2H), 4.09 (d, 2H), 3.91 (s, 3H), 3.82 (t, 1H), 1.49 (2, 18H), 1.32 (s, 9H).

[0387] FIG. 46 shows the .sup.1H NMR spectrum of HL.sub.7 in CDCl.sub.3, 500 MHz.

Synthesis of HL.SUB.8.

[0388] 12 equivalents of NaBH.sub.4 (1.15 g, 30.49 mmol) were added gradually to HL.sub.8 (1.00 g, 2.45 mmol) which was partially dissolved in ethanol (20 mL) over 4 hours, producing a colourless solution. The flask was left to stir overnight and an off-white solid formed. Water (10 mL) was added dropwise to the flask at 0 C. HCl was added to neutralise the solution and the reaction was stirred for an hour. The resulting white solid was filtered and washed with cold water twice. Because some solid appeared in the filtrate, this was re-filtered, washed similarly, and all product was dried in a vacuum oven at 40 C. Isolated Yield: 0.74 g, 1.86 mmol, 74%. .sup.1H NMR (400 MHz, CDCl.sub.3) (ppm): 10.63 (s, 1H), 7.50-7.23 (m, 15H), 6.83-6.80 (d, 1H), 6.72 (t, 1H), 6.53-6.51 (s, 1H), 3.93 (s, 3H), 3.59 (s, 2H), 2.56 (bs, 1H). .sup.13C{.sup.1H} NMR (125 MHz, CDCl.sub.3) (ppm): 148.3, 146.9, 144.8, 129.0, 128.5, 127.2, 123.9, 121.1, 119.4, 110.8, 72.0, 56.3, 47.0, 31.3.

Fluorinated Methoxy Ligands

[0389] Synthesis of HL.sub.4.sup.F

##STR00020##

[0390] 2-Hydroxy-3-(Trifluoromethoxy)benzaldehyde) (0.50 g, 2.4 mmol) was added to a round bottom flask and dissolved in ethanol (15 mL). 2,6-diisopropylaniline (0.43 g, 2.4 mmol) was added into the stirring solution and his reaction mixture was refluxed for 24 hours resulting in a bright solution. Ethanol was removed and the crude product was recrystallized from DCM. .sup.1H NMR (400 MHz, CDCl.sub.3) (ppm): 13.9 (s, 1H), 8.33 (s, 1H), 7.45 (d, 1H), 7.30 (d, 1H), 7.20 (s, 3H), 6.95 (t, 1H), 2.97 (m, 2H), 1.19 (d, 12H). .sup.19F{.sup.1H} NMR (376 MHz, CDCl.sub.3) (ppm): 58.08

[0391] FIG. 47 shows the .sup.1H NMR spectrum of HL.sub.4.sup.F in CDCl.sub.3, 400 MHz.

Example 9Complex Synthesis

Using Imine Ligands

[0392] Synthesis of [(L.sub.4.sup.F).sub.2Ti(O.sup.iPr).sub.2]

[0393] HL.sub.4.sup.F (0.50 g, 1.37 mmol) and Ti(O.sup.iPr).sub.4 (0.19 g, 0.68 mmol) were dissolved separately in toluene (5 mL and 5 mL, respectively), and cooled to 30 C. in a glovebox freezer. The two solutions were then mixed and allowed to stir for 24 hours. Volatiles were removed in vacuo and hexane (10 mL) was added to the resulting orange-yellow wax. This hexane was removed under vacuum to provide the final complex as a bright orange powder. .sup.1H NMR (400 MHz, CDCl.sub.3) (ppm): 8.05 (s, 2H), 7.25-7.10 (m, 10H), 6.54 (t, 2H), 4.10 (m, 2H), 3.71 (bm, 4H), 1.19-0.24 (bm, 36H). .sup.19F{.sup.1H} (376 MHz, CDCl.sub.3) (ppm): 58.4.

[0394] FIG. 48 shows the .sup.1H NMR spectrum of [(L.sup.F.sub.4).sub.2Ti(O.sup.iPr).sub.2] in CDCl.sub.3, 400 MHz, as well as the .sup.19F{.sup.1H} NMR spectrum comparing HL.sup.F.sub.4 (58.1 ppm) and [(L.sup.F.sub.4).sub.2Ti(O.sup.iPr).sub.2] (58.4).sub.400 MHz in CDCl.sub.3.

Synthesis of [(L.sub.4).sub.2Ti(OEt).sub.2]

[0395] HL.sub.4 (0.5 g, 1.61 mmol) and Ti(OEt).sub.4 (0.18 g, 0.80 mmol) were dissolved separately in toluene (10 mL and 10 mL, respectively), and cooled to 30 C. in a glovebox freezer. The two solutions were then mixed and allowed to stir for 24 hours. Volatiles were removed in vacuo and hexane (10 mL) was added to the resulting orange-yellow solid. This hexane was removed under vacuum to provide the final complex as a bright yellow powder (0.49 g, 0.65 mmol, 81%)..sup.1H NMR (400 MHz, CDCl.sub.3) (ppm): 8.51-8.39 (m, 2H), 7.6-7.45 (bs, 2H), 7.13-7.09 (m, 6H), 6.90 (d, 2H), 6.74 (t, 2H), 4.32 (bs, 4H), 3.94-3.89 (m, 6H), 3.15 (bs, 4H), 1.15-1.03 (m, 30H). *Broad signals as well as shouldering suggests isomerization in solution.

[0396] FIG. 49 shows the .sup.1H NMR spectrum of (L.sub.4).sub.2Ti(OEt).sub.2 in CDCl.sub.3 at 298 K.

[0397] FIG. 50 shows the .sup.13C{.sup.1H} NMR spectrum of (L.sub.4).sub.2Ti(OEt).sub.2 in CDCl.sub.3 at 298 K.

Synthesis of [(L.sub.4).sub.2Ti(NMe.sub.2).sub.2]

[0398] HL.sub.4 (2 eq.) and Ti(NMe.sub.2).sub.4 (1 eq) were dissolved separately in toluene (10 mL and 10 mL, respectively), and cooled to 30 C. in a glovebox freezer. The two solutions were then mixed and allowed to stir for 24 hours. Volatiles were removed in vacuo and hexane (10 mL) was added to the resulting red solid. Hexane was removed under vacuum to provide the final complex as a dark red powder. Crystals suitable for XRD were grown from slow evaporation of CDCl.sub.3. .sup.1H NMR was inconclusive, most likely due to fluxionality in the catalyst.

Using Amine Ligands

General Synthesis

[0399] The appropriate amine ligand and Ti(O.sup.iPr).sub.4 in a 2:1 molar ratio, were dissolved separately in toluene (20 mL and 5 mL, respectively), and cooled in a glovebox freezer to 30 C. The dissolved ligand was added slowly to the Ti(O.sup.iPr).sub.4 solution in a Schlenk flask. After stirring for 24 hours, volatiles were removed under vacuum, and the resulting solid was twice dissolved in hexane and dried under vacuum to yield a coloured solid.

Synthesis of [(L.sub.4).sub.2Ti(O.sup.iPr).sub.2]

[0400] HL.sub.4 (1.00 g, 3.19 mmol) was reacted with Ti(O.sup.iPr).sub.4 (0.45 g, 1.60 mmol) to give a yellow powder. Isolated Yield: 0.98 g, 1.20 mmol, 75%..sup.1H NMR (400 MHz, CDCl.sub.3) (ppm): 7.35-7.26 (m, 6H), 7.20-7.18 (m, 2H), 6.89-6.88 (m, 4H), 5.00 (septet, 2H), 4.26-4.24 (d, 4H), 4.04 (s, 6H), 3.91-3.87 (t, 2H), 3.75 (septet, 4H), 1.50-1.44 (m, 36H). .sup.13C{.sup.1H} NMR (125 MHz, CDCl.sub.3) (ppm): 152.3, 149.4, 143.9, 143.3, 126.0, 124.1, 123.9, 123.4, 117.8, 109.1, 80.2, 57.1, 51.6, 27.9, 26.0, 24.8.

[0401] FIG. 51 shows the .sup.1H NMR spectrum of (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 298 K.

[0402] FIG. 52 shows the .sup.13C{.sup.1H} NMR spectrum of (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 298 K.

Synthesis of [(L.sub.5).sub.2Ti(O.sup.iPr).sub.2]

[0403] HL.sub.5 (0.40 g, 1.31 mmol) was reacted with Ti(O.sup.iPr).sub.4 (0.19 g, 1.31 mmol) to give a pale-yellow powder. Isolated Yield: 0.23 g, 0.30 mmol, 46%. .sup.1H NMR (400 MHz, CDCl.sub.3): 7.52-7.45 (m, 8H), 7.36 (m, 2H), 7.23 (m, 2H), 7.14-7.13 (dd, 2H), 6.96-6.95 (dd, 2H), 6.83 (d, 2H), 6.79 (td, 2H), 6.68-6.63 (m, 4H), 4.78 (septet, 2H), 4.50 (t, 2H), 4.38 (d, 4H), 3.7 (s, 6H), 1.23 (d, 12H). .sup.13C{.sup.1H} NMR (125 MHz, CDCl.sub.3) (ppm): 151.8, 148.8, 145.3, 139.8, 130.3, 129.4, 128.9, 128.7, 127.5, 127.1, 124.7, 122.2, 117.3, 116.8, 110.8, 108.5, 80.0, 56.8, 43.1, 25.5.

[0404] FIG. 53 shows the .sup.1H NMR spectrum of (L.sub.5).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 298 K.

[0405] FIG. 54 shows the .sup.13C{.sup.1H} NMR spectrum of (L.sub.5).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 298 K.

Synthesis of [(L.sub.6).sub.2Ti(O.sup.iPr).sub.2]

[0406] HL.sub.6 (2.00 g, 6.96 mmol) was reacted with Ti(O.sup.iPr).sub.4 (0.99 g, 6.96 mmol) to give an orange solid. Isolated Yield: 1.60 g, 2.16 mmol, 62%. .sup.1H NMR (400 MHz, CDCl.sub.3): 6.90 (d, 2H), 6.65-6.60 (m, 4H), 4.84 (septet, 2H), 3.83 (s, 6H), 3.77 (d, 4H), 2.10 (s, 6H), 1.78-1.66 (m, 30H), 1.26 (d, 12H). .sup.13C{.sup.1H} NMR (125 MHz, CDCl.sub.3) (ppm): 152.1, 149.0, 127.1, 123.5, 117.5, 108.5, 79.8, 57.0, 50.8, 43.0, 41.3, 37.1, 29.9, 25.9.

[0407] FIG. 55 shows the .sup.1H NMR spectrum of (L.sub.6).sub.2Ti(O.sup.iPO.sub.2 in CDCl.sub.3 at 298 K.

[0408] FIG. 56 shows the .sup.13C{.sup.1H} NMR spectrum of (L.sub.6).sub.2Ti(O.sup.iPO.sub.2 in CDCl.sub.3 at 298 K.

Synthesis of [(L.sub.7).sub.2Ti(O.sup.iPr).sub.2]

[0409] HL.sub.7 (0.80 g, 2.02 mmol) was reacted with Ti(O.sup.iPr).sub.4 (0.29 g, 1.01 mmol) to give a yellow solid. Isolated Yield: 0.749 g, 0.780 mmol, 77%. .sup.1H NMR (400 MHz, CDCl.sub.3): 7.40 (s, 4H), 7.14 (d, 2H), 6.74 (m, 4H), 4.71 (m, 2H), 4.08 (m, 6H), 3.90 (s, 6H), 1.58 (s, 36H), 1.39 (s, 18H), 1.20 (d, 12H).

[0410] FIG. 57 shows the .sup.1H NMR spectrum of (L.sub.7).sub.2Ti(O.sup.iPr).sub.2 in CDCl.sub.3 at 298 K. 400 MHz.

Example 10Crystallodraphic Studies

[0411] The structure of the complexes prepared from amine ligands could in some cases be confirmed by X-ray crystallography and are shown to adopt Type C coordination (O,O/O,O coordination, Scheme 3). FIG. 58 shows the X-ray crystal structures of (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 (top) and (L.sub.7).sub.2Ti(O.sup.iPr).sub.2 (bottom) showing Type C coordination.

[0412] Having regard to FIGS. 59 to 61, the .sup.1H NMR spectra of (L.sub.4-6).sub.2Ti(O.sup.iPO.sub.2 remain virtually unchanged upon cooling (R.T. to 80 C.) or heating (R.T. to 80 C.) confirming (based on the assignment of the R.T. .sup.1H NMR and the solid state structures of (L.sub.4-6).sub.2Ti(O.sup.iPr).sub.2) that 1) all of these catalysts contain Type C coordination 2) and these catalysts retain this coordination chemistry from 80 C. to 80 C.

[0413] The initiating group on the titanium could be changed from isopropoxide to ethoxide or dimethylamide by changing the titanium precursor to Ti(OEt).sub.4 or Ti(NMe.sub.2).sub.4, thus yielding (L.sub.4).sub.2Ti(OEt).sub.2 and (L.sub.4).sub.2Ti(NMe.sub.2).sub.2 respectively. The structures of these compounds were confirmed using x-ray crystallography. FIG. 62 suggests that changing the steric bulk of the initiating group has an effect on the observed coordination type.

Example 11Polymerisation Studies

[0414] Amide catalysts (L.sub.4-6).sub.2Ti(O.sup.iPO.sub.2 were tested for ethylene polymerization in solution with MAO as an initiator and in the slurry phase after being preimmobilized on sMAO (according to the procedure described in Example 6).

[0415] Polymerization in the solution phase was carried out as follows: MAO (mole ratio 1000:1, Al:Ti) and n-hexane (50 mL) were added to a high-pressure Rotaflo ampoule. To this 1 mg of complex was introduced by adding 200 L of a 1 mL stock solution containing 5 mg solid. After degassing the headspace of the ampoule, ethylene (2 bar) was passed to the flask heated at 80 C. for 5 minutes, after which time the ethylene was removed under vacuum, and the flask was taken out of the oil bath. The sticky solid formed on the stirrer bar was filtered, washed with pentane and dried.

[0416] Polymerization in the slurry phase was carried out according to the following procedure: Triisobutylaluminium (TIBA) (150 mg, 0.76 mmol) in 10 mL n-hexane was used to wash the inside of a high-pressure Rotaflo ampoule. Supported complex (10 mg, 7.4510.sup.4 mmol Ti) was then added, and the solid washed into the flask with a further 40 mL n-hexane. After degassing the headspace, ethylene (2 bar) was passed into the flask and heated at 80 C. for 30 minutes, after which time the reaction was stopped by removing the ethylene under vacuum, and the ampoule was taken out of the oil bath. The resulting solid was filtered, washed with pentane, and dried under vacuum. The yield was calculated from the total solid mass minus the mass of supported catalyst used (10 mg).

[0417] FIG. 63 illustrates the activity of the tested catalysts, as well as the morphology of the obtained polyethylene (PE). It is clear from FIG. 63 that the PE produced on sMAO showed relatively uniform morphology in the SEM where the PE produced from solution phase polymerization was less uniform. The melting temperature of PE derived from slurry phase polymerization was uniformly higher than the corresponding solution phase polymerization. In addition, PE derived from slurry phase polymerization could be annealed through slow cooling cycles in order to increase the melt temperature of the final product by 2-3 C. (Table 5).

TABLE-US-00005 TABLE 5 Melt temperature of pre- and post-annealed polyethylenes prepared by slurry and solution phase polymerisation Catalyst T.sub.m/ C. T.sub.m/ C. (L.sub.4).sub.2Ti(O.sup.iPr).sub.2(sMAO) Pre-anneal 133.8 +3.4 Post-anneal 137.2 (L.sub.4).sub.2Ti(O.sup.iPr).sub.2(Solution) Pre-anneal 130.7 0.0 Post-anneal 130.7 (L.sub.5).sub.2Ti(O.sup.iPr).sub.2(sMAO) Pre-anneal 132.4 +4.6 Post-anneal 137.0 (L.sub.5).sub.2Ti(O.sup.iPr).sub.2(Solution) Pre-anneal 129.9 0.3 Post-anneal 129.6 (L.sub.6).sub.2Ti(O.sup.iPr).sub.2(sMAO) Pre-anneal 136.0 +2.0 Post-anneal 138.0 (L.sub.6).sub.2Ti(O.sup.iPr).sub.2(Solution) Pre-anneal 128.6 0.1 Post-anneal 128.5

[0418] In a separate experiment, the carbocation, [Ph.sub.3C][B(PhF.sub.5).sub.4], in conjunction with triisobutylaluminum, was able to initiate the polymerization of ethylene in (L.sub.4).sub.2Ti(O.sup.iPr).sub.2 and (L.sub.6).sub.2Ti(O.sup.iPr).sub.2. The PE produced was a free-flowing off-white powder with a melting point of 130 C.

[0419] In a separate experiment, (L.sub.4-6).sub.2Ti(O.sup.iPO.sub.2 and (L.sub.4).sub.2Ti(O.sup.iPO.sub.2 were tested at elevated pressure and over a variety of temperatures. These high pressure experiments were carried out according to the following procedure: Triisobutylaluminium (TIBA) (600 mg, 3 mmol) as injected into a 1 L stainless steel high pressure reaction vessel along with 18 700 mL of hexane. The desired amount of supported catalyst (0.03-0.05 g) was then added along with 50 mL of hexane. The reaction vessel was then heated to the desired temperature and pressurised with ethylene. After the desired reaction time the resulting polymer was filtered and allowed to dry for at least 12 hours.

[0420] It is clear from FIG. 64 that all catalysts were active for the polymerization of ethylene following the order: (L.sub.4).sub.2Ti(OiPO.sub.2<(L.sub.4).sub.2Ti(OiPO.sub.2<(L.sub.6).sub.2Ti(OiPO.sub.2. The catalysts were also shown to be active in the presence of comonomers such as 1-hexene, methyl methacrylate and styrene.

[0421] While specific embodiments of the invention have been described herein for the purpose of reference and illustration, various modifications will be apparent to a person skilled in the art without departing from the scope of the invention as defined by the appended claims.

REFERENCES

[0422] 1. Sheldrick, G. M., A short history of SHELX. Acta Crystallographica Section A: Foundations of Crystallography 2008, 64, 112-122. [0423] 2. Farrugia, L. J., WinGX and ORTEP for Windows: an update. Journal of Applied Crystallography 2012, 45, 849-854. [0424] 3. Wilson, A. J. C., International Tables for Crystallography. 1st ed.; Kluwer Academic Publishers: Dordrecht, 1992; Vol. C.