Trapping of Cp*W(NO)(η2-PhC≡CH), the key intermediate in the C-H activation of alkanes by Cp*W(NO)(CH2SiMe3)(CPh≡CH2)

Organometallics

Volumn 16, Issue 9, 1997, Pages 1825-1827

  Legzdins, Peter ^a   Lumb, Sean A ^a  

^a UNIVERSITY OF BRITISH COLUMBIA   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000697980     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om970118x     Document Type: Article

References (26)

1. Debad, J. D.; Legzdins, P.; Lumb, S. A. J. Am. Chem. Soc. 1995, 117, 3288.
2. Coupling reactions of acetylenes and unsaturated organic molecules in metal coordination spheres have been reported previously; see: (a) Broene, R. D.; Buchwald, S. L. Science 1993, 261, 1696. (b) Buchwald, S. L.; Neilsen, R. B. Chem. Rev. 1988, 88, 1047. (c) Maier, M. E.; Oost, T. J. Organomet. Chem. 1995, 505, 95. (d) Peulecke, N.; Ohff, A.; Baumann, W.; Kempe, R.; Burlakov, V. V.; Rosenthal, U. Organometallics 1996, 15, 1340.
3. Coupling reactions of acetylenes and unsaturated organic molecules in metal coordination spheres have been reported previously; see: (a) Broene, R. D.; Buchwald, S. L. Science 1993, 261, 1696. (b) Buchwald, S. L.; Neilsen, R. B. Chem. Rev. 1988, 88, 1047. (c) Maier, M. E.; Oost, T. J. Organomet. Chem. 1995, 505, 95. (d) Peulecke, N.; Ohff, A.; Baumann, W.; Kempe, R.; Burlakov, V. V.; Rosenthal, U. Organometallics 1996, 15, 1340.
4. Coupling reactions of acetylenes and unsaturated organic molecules in metal coordination spheres have been reported previously; see: (a) Broene, R. D.; Buchwald, S. L. Science 1993, 261, 1696. (b) Buchwald, S. L.; Neilsen, R. B. Chem. Rev. 1988, 88, 1047. (c) Maier, M. E.; Oost, T. J. Organomet. Chem. 1995, 505, 95. (d) Peulecke, N.; Ohff, A.; Baumann, W.; Kempe, R.; Burlakov, V. V.; Rosenthal, U. Organometallics 1996, 15, 1340.
5. Coupling reactions of acetylenes and unsaturated organic molecules in metal coordination spheres have been reported previously; see: (a) Broene, R. D.; Buchwald, S. L. Science 1993, 261, 1696. (b) Buchwald, S. L.; Neilsen, R. B. Chem. Rev. 1988, 88, 1047. (c) Maier, M. E.; Oost, T. J. Organomet. Chem. 1995, 505, 95. (d) Peulecke, N.; Ohff, A.; Baumann, W.; Kempe, R.; Burlakov, V. V.; Rosenthal, U. Organometallics 1996, 15, 1340.
6. +; see: Arndtsen, B. A.; Bergman, R. G. Science 1995, 270, 1970.
7. 1H NMR spectroscopic monitoring.
8. Nakamoto, K. Infrared and Roman Spectra of Inorganic and Coordination Compounds, 4th ed.; Wiley-Interscience: New York, 1986.
9. Debad, J. D.; Legzdins, P.; Lumb, S. A. Organometallics 1995, 14, 2543.
10. Filippou, A. C.; Völkl, C.; Kiprof, P. J. Organomet. Chem. 1991, 415, 375.
11. Yeh, W.-Y.; Ting, C.-S.; Chih, C.-F. J. Organomet, Chem. 1991, 427, 257.
12. Legzdins, P.; Sayers, S. J. Am. Chem. Soc. 1994, 116, 12105.
13. Terminal OH ligands in group 6 organometallic complexes are rare, due to their propensity to form very stable bridging oxo ligands by protonolysis of metal-ligand linkages; see: (a) Gilje, J. W.; Roesky, H. W. Chem. Rev. 1994, 94, 895. (b) Bergman, R. G. Polyhedron. 1995, 14, 3227.
14. Terminal OH ligands in group 6 organometallic complexes are rare, due to their propensity to form very stable bridging oxo ligands by protonolysis of metal-ligand linkages; see: (a) Gilje, J. W.; Roesky, H. W. Chem. Rev. 1994, 94, 895. (b) Bergman, R. G. Polyhedron. 1995, 14, 3227.
15. 3- has Mo=O = 1.697(7) Å and Mo-OH = 2.077(7) Å; see: Robinson, P. R.; Schlemper, E. O.; Murmann, R. K. Inorg. Chem. 1975, 14, 2035. Typical terminal W-oxo bond distances lie in the range 1.68-1.72 Å; see: Nugent, W. A.; Mayer, J. M. Metal Ligand Multiple Bonds; Wiley: New York, 1988.
16. 3- has Mo=O = 1.697(7) Å and Mo-OH = 2.077(7) Å; see: Robinson, P. R.; Schlemper, E. O.; Murmann, R. K. Inorg. Chem. 1975, 14, 2035. Typical terminal W-oxo bond distances lie in the range 1.68-1.72 Å; see: Nugent, W. A.; Mayer, J. M. Metal Ligand Multiple Bonds; Wiley: New York, 1988.
17. Christensen, N. J.; Hunter, A. D.; Legzdins, P. Organometallics 1989, 8, 930.
18. An analogous coupling is observed in the iridapyrrole complex recently reported by Carmona et al.; see: Alvarado, Y.; Daff, P. J.; Pérez, P. J.; Poveda, M. L.; Sánchez-Delgado, R.; Carmona, E. Organometallics 1996, 15, 2192.
19. Aromaticity has been invoked for similar iridium aza- and thiapentadienyl systems; see: (a) Reference 13.
20. (b) Bleeke, J. R.; Ontwerth, M. F.; Rohde, A. M. Organometallics 1995, 14, 2813.
21. Ashby, M. T.; Enemark, J. H. J. Am. Chem. Soc. 1986, 108, 730.
22. For other examples of imide protonation, see: (a) Lorente, P.; Carfangna, C.; Etienne, M.; Donnadieu, B. Organometallics 1996, 15, 1090.
23. (b) Reference 13.
24. Strickler, J. R.; Wigley, D. E. Organometallics 1990, 9, 1665.
25. The formation of 2-4 was monitored by UV-vis spectroscopy and is cleanly first order in 1. Monitoring was effected for not less than 3.5 half-lives, and the temperature was controlled to 44.5 ± 0.25 °C.
26. Connors, K. A. Chemical Kinetics: The Study of Reaction Rates in Solution; VCH: New York, 1990; Chapter 8.