The mechanism of methane elimination in B(C6F5)3-initiated monocyclopentadienyl-ketimide titanium and related olefin polymerization catalysts

Journal of the American Chemical Society

Volumn 122, Issue 23, 2000, Pages 5499-5509

  Zhang, Suobo ^a   Piers, Warren E ^a   Gao, Xiaoliang ^b   Parvez, Masood ^a  

^a UNIVERSITY OF CALGARY   (Canada)

^b NOVA CHEMICALS CORPORATION   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

ALKANE; ALKENE; METHANE; METHYL CHLORIDE; MONOCYCLOPENTADIENYL KETIMIDE TITANIUM; TITANIUM DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; ENTHALPY; LIGAND BINDING; METHYLATION; MOLECULAR DYNAMICS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; POLYMERIZATION; REACTION ANALYSIS;

EID: 0034647240     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja994378c     Document Type: Article

References (90)

1. (a) Mohring, P. C.; Coville, N. J. J. Organomet. Chem. 1994, 479, 1.
2. (b) Brintzinger, H. H.; Fischer, D.; Mulhaupt, R.; Rieger, B.; Waymouth, R. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 1143.
3. (c) Bochmann, M. J. Chem. Soc., Dalton Trans. 1996, 255.
4. (d) Marks, T. J. Acc. Chem. Res. 1992, 25, 57.
5. (e) Jordan, R. F. Adv. Organomet. Chem. 1991, 32, 325.
6. (f) Jordan, R. F.; Bradley, P. K.; LaPointe, R. E.; Taylor, D. F. New J. Chem. 1990, 14, 505.
7. (g) Ziegler Catalysts; Fink, G., Mülhaupt, R., Brintzinger, H. H., Eds.; Springer: Berlin, 1995.
8. (h) Resconi, L.; Cavallo, L.; Fait, A.; Piemontesi, F. Chem. Rev. 2000, 100, 1253.
9. (a) Britovsek, G. P.; Gibson, V. C.; Wass, D. F. Angew. Chem., Int. Ed. 1999, 38, 429.
10. (b) Liang, L.-C.; Schrock, R. R.; Davis, W. M.; McConville, D. H. J. Am. Chem. Soc. 1999, 121, 5797.
11. (c) Baumann, R.; Stumpf, R.; Davis, W. M.; Liang, L.-C.; Schrock, R. R. J. Am. Chem. Soc. 1999, 121, 7822.
12. (a) Piers, W. E.; Shapiro, P. J.; Bunel, E. E.; Bercaw, J. E. Synlett 1990, 1, 74.
13. (b) Shapiro, P. J.; Cotter, W. D.; Schaefer, W. P.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1994, 116, 4623.
14. Stevens, J. C.; Timmers, F. J.; Wilson, D. R.; Schmidt, G. F.; Nickias, P. N.; Rosen, R. K.; Knight, G. W.; Lai, S. European Patent Appl. EP 416 815-A2, 1991 (Dow Chemical Co.).
15. Canich, J. M.; Hlatky, G. G.; Turner, H. W. PCT Appl. WO 92-00333, 1992 (Exxon Chemical Co.).
16. Scollard, J. D.; McConville, D. H.; Vittal, J. J. Macromolecules 1996, 29, 5241.
17. (a) Scollard, J. D.; McConville, D. H. J. Am. Chem. Soc. 1996, 118, 10008.
18. (b) Scollard, J. D.; McConville, D. H.; Vittal, J. J.; Payne, N. C. J. Mol. Catal. A: Chem. 1998, 128, 201.
19. Deng, L.; Ziegler, T.; Woo, T. K.; Margl, P.; Fan, L. Organometallics 1998, 17, 3240.
20. (a) Vilardo, J. S.; Thorn, M. G.; Fanwick, P. E.; Rothwell, I. P. Chem. Commun. 1998, 2425.
21. (b) Thorn, M. G.; Vilardo, J. S.; Fanwick, P. E.; Rothwell, I. P. Chem. Commun. 1998, 2427.
22. (c) Sarsfield, M. J.; Ewart, S. W.; Tremblay, T. L.; Roszak, A. W.; Baird, M. C. J. Chem. Soc., Dalton Trans. 1997, 3097.
23. (d) Ewart, S. W.; Sarsfield, M. J.; Jeremic, D.; Tremblay, T. L.; Williams, E. F.; Baird, M. C. Organometallics 1998, 17, 1502.
24. (e) For a related chelating system see: Chen, Y.-X.; Fu, P.-F.; Stern, C. L.; Marks, T. J. Organometallics 1997, 16, 5958.
25. (a) Mena, M.; Royo, P.; Serrano, R.; Pellinghelli, A.; Tiripicchio, A. Organometallics 1989, 8, 476.
26. (b) Ewart, S. W.; Baird, M. C. Top. Catal. 1999, 7, 1.
27. (a) Bai, Y.; Roesky, H. W.; Noltmeyer, M. Z. Anorg. Allg. Chem. 1991, 31, 3887.
28. (b) Schiffino, R. S.; Crowther, D. J. U.S. patent No. 5,625,016, 1997 (Exxon Chemical).
29. Stephan, D. W.; Stewart, J. C.; Guerin, F.; Spence, R. E. v. H.; Xu, W.; Harrison, D. G. Organometallics 1999, 18, 1116.
30. Klapötke, T.; Laskowski, R.; Köpf, H. Z. Naturforsch., Teil B 1987, 42, 777.
31. Related examples: (a) Richter, J.; Edelmann, F. T.; Noltmeyer, M.; Schmidt, H.-G.; Shmulinson, M.; Eisen, M. S. J. Mol. Catal. A: Chem. 1998, 130, 149. (b) Yoon, S. C.; Bae, B.-J.; Suh, I.-H.; Park, J. T. Organometallics 1999, 18, 2049. (c) Amor, F.; Butt, A.; du Plooy, K. E.; Spaniol, T. P.; Okuda, J. Organometallics 1998, 17, 5836.
32. Related examples: (a) Richter, J.; Edelmann, F. T.; Noltmeyer, M.; Schmidt, H.-G.; Shmulinson, M.; Eisen, M. S. J. Mol. Catal. A: Chem. 1998, 130, 149. (b) Yoon, S. C.; Bae, B.-J.; Suh, I.-H.; Park, J. T. Organometallics 1999, 18, 2049. (c) Amor, F.; Butt, A.; du Plooy, K. E.; Spaniol, T. P.; Okuda, J. Organometallics 1998, 17, 5836.
33. Related examples: (a) Richter, J.; Edelmann, F. T.; Noltmeyer, M.; Schmidt, H.-G.; Shmulinson, M.; Eisen, M. S. J. Mol. Catal. A: Chem. 1998, 130, 149. (b) Yoon, S. C.; Bae, B.-J.; Suh, I.-H.; Park, J. T. Organometallics 1999, 18, 2049. (c) Amor, F.; Butt, A.; du Plooy, K. E.; Spaniol, T. P.; Okuda, J. Organometallics 1998, 17, 5836.
34. (a) Bochmann, M.; Lancaster, S. J. J. Organomet. Chem. 1992, 434, C1.
35. (b) Chien, J. C. W.; Tsai, W. M.; Rausch, M. D. J. Am. Chem. Soc. 1991, 113, 8570.
36. (a) Massey, A. G.; Park, A. J. J. Organomet. Chem. 1966, 5, 218.
37. (b) Piers, W. E.; Chivers, T. Chem. Soc. Rev. 1997, 345.
38. 2] (see Experimental Section).
39. Scollard, J. D.; McConville, D. H.; Rettig, S. J. Organometallics 1997, 16, 1810.
40. Bochmann, M.; Wilson, L. M.; Hursthouse, M. B.; Motevalli, M. Organometallics 1988, 7, 1148.
41. Latham, I. A.; Leigh, G. J.; Huttner, G.; Jibril, I. J. Chem. Soc., Dalton Trans. 1986, 377.
42. McMeeking, J.; Gao, X.; Spence, R. E. v. H.; Brown. S. J.; Jeremic, D. PCT WO 99/14250, 1999 (Nova Chemicals Ltd.).
43. Armstrong, D. R.; Barr, D.; Snaith, R.; Mulvey, R. E.; Wade, K.; Reed, D. J. Chem. Soc., Dalton Trans. 1987, 1071.
44. Waters, J. A.; Mortimer. G. A. J. Organomet. Chem. 1970, 22, 417.
45. Luinstra, G. A.; Teuben, J. H. J. Organomet. Chem. 1991, 420, 337.
46. Stevens, J. C. In Catalyst Design for Tailor Made Polyolefins, Studies in Surface Science and Catalysis; Soga, K., Terano, M., Eds; Elsevier: Amsterdam, 1994; Vol. 89, p 277.
47. Sandstrom, J. Dynamic NMR Spectroscopy; Academic Press: New York, 1982.
48. 2 has been rationalized in this fashion: Giolando, G. M.; Kirschbaum, K.; Graves, L. J.; Bolle, U. Inorg. Chem. 1992, 31, 3887.
49. Gao, X.; Wang, Q. Unpublished results.
50. (a) Horton, A. D. Organometallics 1996, 15, 2675.
51. (b) Beck, S.; Prosenc, M. H.; Brintzinger, H. H. J. Mol. Catal. A: Chem. 1998, 128, 41.
52. (c) Beswick, C. L.; Marks, T. J. Organometallics 1999, 18, 2410.
53. Yang, X.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1994, 116, 10015.
54. (a) Deck, P. A.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 6128.
55. (b) Siedle, A. R.; Newmark, R. A. J. Organomet. Chem. 1995, 497, 119.
56. (c) Chen, Y. X.; Metz, M. V.; Li, L.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1998, 120, 6287.
57. (d) Deck, P. A.; Beswick, C. L.; Marks, T. J. J. Am. Chem. Soc. 1998, 120, 1772.
58. (e) Luo, L.; Marks, T. J. Top. Catal. 1999, 7, 97.
59. 2, the Cp-methyl peaks are close to the fast exchange limit at room temperature, indicating that, as expected, ion pair reorganization is faster in these more polar solvents. Quantitative evaluation of the temperature-dependent spectra was precluded by the onset of decomposition at the higher temperatures necessary to reach the fast exchange limit.
60. Bax, A.; Subramanian, S. J. Magn. Reson. 1986, 67, 565.
61. Thewalt, U.; Worthle, T. J. Organomet. Chem. 1994, 464, C17.
62. Cook, K. S.; Piers, W. E.; Rettig, S. J. Organometallics 1999, 18, 1575.
63. Bochmann, M.; Cuenca, T.; Hardy, D. T. J. Organomet. Chem. 1994, 484, C10.
64. 2 (∈ = 9.08) were hampered by side reactions which we believe involved chloride abstraction from the solvent.
65. Temme, B.; Erker, G. J. Organomet. Chem. 1995, 488, 177.
66. 3, resulted in competitive trimethylsilylmethyl abstraction (≈30%).
67. Scoles, L.; Minhas, R.; Duchateau, R.; Jubb, J.; Gambarotta, S. Organometallics 1994, 13, 4978.
68. 2, the conclusions here would be the same for a bimolecular elimination of RH.
69. (a) Tebbe, F. N.; Parshall, G. W.; Reddy, G. S. J. Am. Chem. Soc. 1978, 100, 3611.
70. (b) Tebbe, F. N.; Harlow, R. L. J. Am. Chem. Soc. 1980, 102, 6149.
71. (c) Ott, K. C.; deBoer, E. J. M.; Grubbs, R. H. Organometallics 1984, 3, 223.
72. Thompson, M. E.; Baxter, S. M.; Bulls, A. R.; Burger, B. J.; Nolan, M. C.; Santarsiero, B. D.; Schaefer, W, P.; Bercaw, J. E. J. Am. Chem. Soc. 1987, 109, 203 and references therein.
73. (a) Jordan, R. F.; Taylor, D. F.; Baenziger, N. C. Organometallics 1990, 9, 1546.
74. (b) Jordan, R. F.; LaPointe, R. E.; Bradley, P. K.; Baenziger, N. C. Organometallics 1989, 8, 2892.
75. (c) Siedle, A. R.; Lamanna, W. M.; Newmark, R. A.; Schroepfer, J. N. J. Mol. Catal. A: Chem. 1998, 128, 257.
76. (d) Eshuis, J. J. W.; Tan, Y. Y.; Meetsma, A.; Teuben, J. H.; Renkema, J.; Evens, G. G. Organometallics 1992, 11, 362.
77. Spence R. E. v H.; Piers, W. E.; Sun, Y.; Parvez, M.; MacGillivray, L. R.; Zaworotko, M. J. Organometallics 1998, 17, 2459.
78. Lambert, J. B. Tetrahedron 1990, 46, 2677.
79. Eisch, J. J.; Piotrowski, A. M.; Brownstein, S. K.; Gabe, E. J.; Lee, F. L. J. Am. Chem. Soc. 1985, 107, 7219.
80. Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1988, 110, 108.
81. (a) Kaminsky, W.; Steiger, R. Polyhedron 1988, 7, 2375.
82. (b) Kaminsky, W.; Bark, A.; Steiger, R. J. Mol Catal. 1992, 74, 109.
83. Reddy, S. S.; Shasidhar, G.; Sivaram, S. Macromolecules 1993, 26, 1180.
84. Burger, B. J.; Bercaw, J. E. Experimental Organometallic Chemistry; Wayda, A. L., Darensbourg, M. Y., Eds.; ACS Symp. Ser. 357; American Chemical Society: Washington, DC, 1987.
85. Pangborn, A. B.; Giardello, M. A.; Grubbs, R. H.; Rosen, R. K.; Timmers, F. J. Organometallics 1996, 15, 1518.
86. Marvich, R. H.; Brintzinger, H. H. J. Am. Chem. Soc. 1971, 93, 2046.
87. Courtot, P.; Pichon, R.; Salaun, J. Y.; Toupet, L. Can. J. Chem. 1991, 69, 661.
88. Mena, M.; Royo, P.; Serrano, R.; Pellinghell, M. A.; Tiripicchio, A. Organometallics 1989, 8, 476.
89. Hitchcock, P. B.; Lappert, M. F.; Layh, M. J. Organomet. Chem. 1997, 529, 243.
90. Crystal Structure Analysis Package, Molecular Structure Corporation, 1985 and 1992.