Synthesis, structures, and kinetics and mechanism of decomposition of terminal metal azide complexes: Isolated intermediates in the formation of imidometal complexes from organic azides

Organometallics

Volumn 15, Issue 2, 1996, Pages 684-692

  Proulx, Grant ^a   Bergman, Robert G ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000258995     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om950796o     Document Type: Article

References (32)

1. (a) Nugent, W. A.; Mayer, J. M. Metal-Ligand Multiple Bonds; John Wiley and Sons: New York, 1988.
2. (b) Wigley, D. E. Prog. Inorg. Chem. 1994, 42, 239.
3. Cummins, C. C.; Baxter, S. M.; Wolczanski, P. T. J. Am. Chem. Soc. 1988, 110, 8731.
4. Walsh, P. J.; Hollander, F. J.; Bergman, R. G. J. Am. Chem. Soc. 1988, 110, 8731.
5. Cummins, C. C.; Schaller, C. P.; VanDuyne, G. D.; Wolcazanski, P. T.; Chan, A. W. E.; Huffman, R. J. Am. Chem. Soc. 1991, 113, 2985.
6. Lwowski, W. Nitrenes; Interscience Publishers: New York, 1970.
7. Hillhouse, G. L.; Haymore, B. L. J. Am. Chem. Soc. 1982, 104, 1537.
8. Antonelli, D. M.; Schaefer, W. P.; Parkin, G.; Bercaw, J. E. J. Organomet. Chem. 1993, 462, 213.
9. Gambarotta, S.; Chiesi-Villa, A.; Guastini, C. J. Organomet. Chem. 1984, 270, C49.
10. Hillhouse, G. L.; Goeden, G. V.; Haymore, B. L. Inorg. Chem. 1982, 21, 2064.
11. Rosen, R. K. Ph.D. Thesis, U.C. Berkeley, Berkeley, CA, 1989.
12. Chiu, K. W.; Wilkinson, G.; Thornton-Pett, M.; Hursthouse, M. Polyhedron 1984, 3, 79.
13. Hanna, T. A.; Bergman, R. G. Angew. Chem., submitted for publication.
14. Matsunaga, P. T.; Hess, C. R.; Hillhouse, G. L. J. Am. Chem. Soc. 1994, 116, 3665.
15. Proulx, G.; Bergman, R. G. J. Am. Chem. Soc. 1995, 117, 6382.
16. In a related vanadium organoazide complex discovered simultaneously and independently by Cummins and co-workers, different behavior was observed regarding the azide ligand. In Cummins' system, rapid scrambling of free azide into the bound azide position was found, and second-order kinetics were also observed. Our system does not seem to display either of these characteristics. See: Cummins, C. C.; Fickes, M. J.; Davis, W. M. J. Am. Chem. Soc. 1995, 117, 6384.
17. Schrock, R. R.; Sharp, P. R. J. Am. Chem. Soc. 1978, 100, 2389.
18. Proulx, G.; Bergman, R. G. J. Am. Chem. Soc. 1994, 116, 7953.
19. Parkin, G.; van Asselt, A.; Leahy, D. J.; Whinnery, L.; Hua, N. G.; Quan, R. W.; Henling, L. M.; Schaefer, W. P.; Santarsiero, B. D.; Bercaw, J. E. Inorg. Chem. 1992, 31, 82.
20. Jørgensen, K. A. Inorg. Chem. 1993, 32, 1521.
21. Nugent, W. A.; Harlow, R. L. J. Chem. Soc., Chem. Commun. 1978, 579.
22. Bouwstra, J. A.; Schouten, A.; Kroon, J. Acta Crystallogr., C 1983, 39, 1121.
23. 2 and the results shown to be independent of the additive.
24. 15 is also converted to the corresponding arylimido complex, but the kinetics are second rather than first order. It is possible that this is due to the different electronic character of the vanadium species.
25. Gololobov, Y. G.; Kasukhin, L. F. Tetrahedron 1992, 48, 1353, and references therein.
26. Mosby, W. L.; Silva, M. L. J. Chem. Soc. 1965, 1003.
27. Horner, L.; Gross, A. Justus Liebigs Ann. Chem. 1995, 591, 117.
28. Engel, P. S.; Bishop, D. J. J. Am. Chem. Soc. 1975, 97, 6754.
29. Hostetler, M. J.; Butts, M. D.; Bergman, R. G. J. Am. Chem. Soc. 1993, 115, 2743.
30. Calculations were performed on DEC MicroVax computers using locally modified versions of the Enraf-Nonius Mo1EN structure solution and refinement package and other programs.
31. Roof, R. B. J. A Theoretical Extension of the Reduced-Cell Concept in Crystallography; Publication LA-4038; Los Alamos Scientific Laboratory: Los Alamos, NM, 1969.
32. Walker, N.; Stuart, D. Acta Crystallogr. 1983, A39, 159.