Reversible migratory insertion/β-alkyl elimination in α-agostic alkylniobium alkyne complexes

Journal of the American Chemical Society

Volumn 119, Issue 14, 1997, Pages 3218-3228

  Etienne, Michel ^a   Mathieu, René ^a   Donnadieu, Bruno ^a  

^a LCC LABORATOIRE DE CHIMIE DE COORDINATION   (France)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYNE DERIVATIVE; METAL COMPLEX; NIOBIUM;

ARTICLE; COMPLEX FORMATION; CRYSTALLOGRAPHY; IN VITRO STUDY; NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS;

EID: 0030921304     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja963697q     Document Type: Article

References (60)

1. (a) Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G. Principles and Applications of Organotransition Metal Chemistry; University Science Books: Mill Valley, 1987.
2. (b) Otsuka, S.; Nakamura, A. Adv. Organomet. Chem. 1976, 14, 245.
3. (c) Comprehensive Organometallic Chemistry; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: Oxford, U.K., 1982; Vol. 8.
4. (d) Comprehensive Organometallic Chemistry II; Hegedus, L. S., Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: Oxford, U.K., 1995; Vol. 12.
5. (e) Huggins, J. H.; Bergman, R. G. J. Am. Chem. Soc. 1981, 103, 3002.
6. (a) Fink, G., Mülhaupt, R., Brintzinger, H.-H., Eds. Ziegler Catalysts; Springer-Verlag: Berlin, 1995.
7. (b) Brintzinger, H.-H.; Fischer, D.; Mülhaupt, R.; Rieger, B.; Waymouth, R. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 1143.
8. (c) Jordan, R. F. Adv. Organomet. Chem. 1991, 32, 325.
9. (d) Bochman, M. J. Chem. Soc., Dalton Trans. 1996, 255.
10. Cotter, W. D.; Bercaw, J. E. J. Organomet. Chem. 1991, 417, C1.
11. Eisch, J. J.; Piotrowski, A. M.; Brownstein, S. K.; Gabe, E. J.; Lee, F. L. J. Am. Chem. Soc. 1985, 107, 7219.
12. Jordan, R. F.; Lapointe, R. E.; Bradley, P. K.; Baezinger, N. Organometallics 1989, 8, 2892.
13. Templeton, J. L. Adv. Organomet. Chem. 1989, 29, 1.
14. Yasuda, H.; Yamamoto, H.; Arai, T.; Nakamura, A.; Chen, J.; Kai, Y.; Kasai, N. Organometallics 1991, 10, 4058.
15. Curtis, M. D.; Real, J.; Hirpo, W.; Buthler, W. M. Organometallics 1990, 9, 66.
16. Hirpo, W.; Curtis, M. D. Organometallics 1994, 13, 2706.
17. (a) Hajela, S.; Bercaw, J. E. Organometallics 1994, 13, 1147.
18. (b) Sini, G.; Macgregor, S. A.; Eisenstein, O.; Teuben, J. H. Organometallics 1994, 13, 1049.
19. (c) Resconi, L.; Piemontesi, F.; Franciscono, G.; Abis, L.; Fiorani, T. J. Am. Chem. Soc. 1992, 114, 1025.
20. (d) Yang, X.; Jia, L.; Marks, T. J. J. Am. Chem. Soc. 1993, 115, 3392.
21. (e) Watson, P. L.; Parshall, G. W. Acc. Chem. Res. 1985, 18, 521.
22. (f) Horton, A. D. Organometallics 1996, 15, 2675.
23. Brookhart, M.; Green, M. L. H.; Wong, L.-L. Prog. Inorg. Chem. 1988, 36, 1.
24. Grubbs, R. H.; Coates, G. W. Acc. Chem. Res. 1996, 29, 85.
25. Etienne, M.; Biasotto, F.; Mathieu, R. J. Chem. Soc., Chem. Commun. 1994, 1661.
26. Etienne, M.; Biasotto, F.; Mathieu, R.; Templeton, J. L. Organometallics 1996, 15, 1106.
27. Poole, A. D.; Williams, D. N.; Kenwright, A. M.; Gibson, V. C.; Clegg, W.; Hockless, C. R.; O'Neil, P. A. Organometallics 1993, 12, 2549.
28. Rheingold, A. L.; Ostrander, R. L.; Haggerty, B. S.; Trofimenko, S. Inorg. Chem. 1994, 33, 3666.
29. Guo, Z.; Swenson, D. C.; Jordan, R. F. Organometallics 1994, 13, 1424.
30. Calvert, R. B.; Shapley, J. P. J. Am. Chem. Soc. 1978, 100, 7726.
31. Dawoodi, Z.; Green, M. L. H.; Mtetwa, V. S. B.; Prout, K.; Schultz, A. J.; Williams, J. M.; Koetzle, T. J. Chem. Soc., Dalton Trans. 1986, 1629.
32. Green, M. L. H.; Hugues, A. K.; Popham, N. A.; Stephens, A. H. H.; Wong, L.-L. J. Chem. Soc., Dalton Trans. 1992, 3077.
33. Maus, D. C.; Copié, V.; Sun, B.; Griffiths, J. M.; Griffin, R. G.; Luo, S.; Schrock, R. R.; Liu, A. H.; Seidel, S. W.; Davis, W. M.; Grohman, A. J. Am. Chem. Soc. 1996, 118, 5665.
34. 2(HC≡CH). To a first approximation, this indicates electronic saturation despite the formal 16e-count. Thus we suggest that the higher alkyl complexes 2a-e, 3b,c, and 4a are α-agostic mainly because of important steric repulsions between the alkyl groups and Tp*. The methyl group would be small enough so that no steric pressure would force any α-agostic interaction. See: Etienne, M.; Donnadieu, B.; Mathieu, R.; Fernandez-Baeza, J.; Jalon, F.; Otero, O.; Rodrigo-Blanco, M. E. Organometallics 1996, 15, 4597.
35. Etienne, M. Organometallics 1994, 13, 410.
36. Herberich, G. E.; Mayer, H. Organometallics 1990, 9, 2655.
37. Mc Neill, K.; Andersen, R. A.; Bergman, R. G. J. Am. Chem. Soc. 1995, 117, 3625.
38. Wigley, D. E. Prog. Inorg. Chem. 1994, 42, 239.
39. Leroux, Y.; Burgada, R.; Kleeman, S. G.; Fluck, E. In CRC Handbook of Phosphorus-31 Nuclear Magnetic Resonance Data; Tebby, J. C., Ed.; CRC Press: Boca Raton, FL, 1987; p 93.
40. Dehnicke, K.; Strahle, J. Chem. Rev. 1993, 93, 981.
41. Sutton, D. Chem. Rev. 1993, 93, 995.
42. Bishop, M. W.; Chan, J.; Dilworth, J. R.; Hursthouse, M. B.; Motevalle, M. J. Less-Common Met. 1977, 54, 487.
43. Green, M. L. H.; James, J. T.; Sanders, J. F. Chem. Commun. 1996, 1343.
44. (a) Dehnicke, K.; Strahle, J. Polyhedron 1989, 8, 707.
45. (b) Weller, F.; Nusshar, D.; Dehnicke, K. Z. Anorg. Allg. Chem. 1992, 615, 7.
46. (c) Olms, P.; Roesky, H. W.; Keller, K.; Noltemeyer, M. Z Naturforsch., Teil B 1992, 47, 1609.
47. (d) Nusszhar, D.; Weller, F.; Dehnicke, K.; Hiller, W. J. Alloys Compds. 1992, 183, 30.
48. Cockcroft, J. K.; Gibson, V. C., Howard, J. A. K.; Poole, A. D.; Siemeling, U.; Wilson, C. J. Chem. Soc., Chem. Commun. 1992, 1668.
49. Whinnery, L. L.; Henling, L. M.; Bercaw, J. E. J. Am. Chem. Soc. 1991, 113, 7575.
50. Proulx, G.; Bergman, R. G. Organometallics 1996, 15, 133.
51. Cummins, C. C.; Schrock, R. R.; Davis, W. M. Inorg. Chem. 1994, 73, 1448.
52. (a) Reger, D. L.; Belmore, K. A.; Mintz, E.; McElligott, P. J. Organometallics 1984, 3, 134.
53. (b) Reger, D. L. Acc. Chem. Res. 1988, 21, 229.
54. Allen, S. R.; Beevor, R. G.; Green, M.; Norman, N. C.; Orpen, A. G.; Williams, I. D. J. Chem. Soc., Dalton Trans. 1985, 435.
55. (a) Burger, B. J.; Santarsiero, B. D.; Trimmer M. S.; Bercaw, J. E. J. Am. Chem. Soc. 1988, 110, 3134.
56. (b) Brookhart, M.; Hauptman, E.; Lincoln, D. M. J. Am. Chem. Soc. 1992, 114, 10394.
57. (a) Rix, F.; Brookhart, M. J. Am. Chem. Soc. 1995, 117, 1137.
58. (b) Rix, F. C.; Brookhart, M.; White, P. S. J. Am. Chem. Soc. 1996, 118, 4746.
59. Dias, A. R.; Diogo, H. P.; Griller, D.; Minas de Piedade, M. E.; Martinho Simoes, J. A. In Bonding Energetics in Organometallic Compounds; ACS Symposium Series 428; Marks, T. J., Ed.; American Chemical Society: Washington, DC, 1990; pp 205-217.
60. Scherer, O. J.; Glabel, W. Chem. Ztg. 1975, 99, 246.