Dimerization of rhenium alkynyl carbene complexes by a process involving two [1,1.5] Rhenium shifts and coupling of the remote alkynyl carbons [1]

Journal of the American Chemical Society

Volumn 122, Issue 15, 2000, Pages 3771-3772

  Casey, Charles P ^a   Kraft, Stefan ^a   Powell, Douglas R ^a  

^a UNIVERSITY OF WISCONSIN MADISON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYNYL GROUP; CARBENE; CARBON; RHENIUM;

COMPLEX FORMATION; DIMERIZATION; LETTER; PROTON NUCLEAR MAGNETIC RESONANCE; X RAY DIFFRACTION;

EID: 0034685470     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9945010     Document Type: Letter

References (26)

1. For heteroatom-substituted alkynyl carbene complexes, see: (a) Aumann, R.; Nienaber, H. Adv. Organomet. Chem. 1997, 41, 161. (b) Wulff, W. D. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford, 1995; Vol. 12, Chapter 5.3. (c) Herndon, J. W. Coord. Chem. Rev. 1999, 181, 177.
2. For heteroatom-substituted alkynyl carbene complexes, see: (a) Aumann, R.; Nienaber, H. Adv. Organomet. Chem. 1997, 41, 161. (b) Wulff, W. D. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford, 1995; Vol. 12, Chapter 5.3. (c) Herndon, J. W. Coord. Chem. Rev. 1999, 181, 177.
3. For heteroatom-substituted alkynyl carbene complexes, see: (a) Aumann, R.; Nienaber, H. Adv. Organomet. Chem. 1997, 41, 161. (b) Wulff, W. D. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford, 1995; Vol. 12, Chapter 5.3. (c) Herndon, J. W. Coord. Chem. Rev. 1999, 181, 177.
4. A [1,3] shift was postulated in a rhodium alkynyl carbene presumably formed in a catalytic cycle: Padwa, A.; Austin, D. J.; Gareau, Y.; Kassir, J. M.; Xu, S. L. J. Am. Chem. Soc. 1993, 115, 2637.
5. 5 carbene complexes. (a) Casey, C. P.; Vosejpka, P. C.; Askham, F. R. J. Am. Chem. Soc. 1990, 112, 3713. (b) Casey, C. P.; Czerwinski, C. J.; Powell, D. R.; Hayashi, R. K. J. Am. Chem. Soc. 1997, 119, 5750. (c) Iwasawa, N.; Maeyama, K.; Saitou, M. J. Am. Chem. Soc. 1997, 119, 1486.
6. 5 carbene complexes. (a) Casey, C. P.; Vosejpka, P. C.; Askham, F. R. J. Am. Chem. Soc. 1990, 112, 3713. (b) Casey, C. P.; Czerwinski, C. J.; Powell, D. R.; Hayashi, R. K. J. Am. Chem. Soc. 1997, 119, 5750. (c) Iwasawa, N.; Maeyama, K.; Saitou, M. J. Am. Chem. Soc. 1997, 119, 1486.
7. 5 carbene complexes. (a) Casey, C. P.; Vosejpka, P. C.; Askham, F. R. J. Am. Chem. Soc. 1990, 112, 3713. (b) Casey, C. P.; Czerwinski, C. J.; Powell, D. R.; Hayashi, R. K. J. Am. Chem. Soc. 1997, 119, 5750. (c) Iwasawa, N.; Maeyama, K.; Saitou, M. J. Am. Chem. Soc. 1997, 119, 1486.
8. We introduce the term "[1,1.5] shift" to describe the migration of rhenium from carbon 1 of carbene complex 1 to the midpoint between carbons 1 and 2 of the resulting alkyne complex 4.
9. 2 carbyne complex, see: Fischer, E. O.; Clough, R. L.; Stückler, P. J. Organomet. Chem. 1976, 120, C6.
10. 3-symmetric geometry in which the plane of the carbene ligand is nearly perpendicular to the plane of the Cp ring. The alkynyl unit is syn to the Cp ligand. See Supporting Information.
11. 13C≡CTol). See Supporting Information.
12. 2 and thermal decomposition of 4 is a first-order process.
13. Addition of lithium or zinc reagents to alkynyl carbene complexes has led to formation of bimetallic compounds, (a) Dötz, K. H.; Christoffers, C.; Knochel, P. J. Organomet. Chem. 1995, 489, C84. (b) Fischer, H.; Meisner, T.; Hofmann, J. Chem. Ber. 1990, 123, 1799.
14. Addition of lithium or zinc reagents to alkynyl carbene complexes has led to formation of bimetallic compounds, (a) Dötz, K. H.; Christoffers, C.; Knochel, P. J. Organomet. Chem. 1995, 489, C84. (b) Fischer, H.; Meisner, T.; Hofmann, J. Chem. Ber. 1990, 123, 1799.
15. 13CPh). See Supporting Information.
16. (a) Casey, C. P.; Anderson, R. L. J. Chem. Soc., Chem. Commun. 1975, 895.
17. (b) Fischer, H., Schmid, J. J. Mol. Catal. 1988, 46, 277.
18. (c) Hohmann, F.; Siemoneit, S.; Nieger, M.; Kotila, S.; Dötz, K. H.; Chem. Eur. J. 1997, 3, 853.
19. - to a cyclopropenylidene complex. Juneau, K. N.; Hegedus, L. S.; Roepke, F. W. J. Am. Chem. Soc. 1989, 111, 4762.
20. Note that D is a resonance structure of B.
21. 5 times more reactive toward nucleophiles than alkyl tosylates, the electrophilicity of 1 lies between methyl triflate and methyl tosylate. (a) Stang, P. J.; Hanack, M.; Subramanian, L. R. Synthesis 1982, 85. (b) Su, T. M.; Sliwinski, W. F.; Schleyer, P. v. R. J. Am. Chem. Soc. 1969, 91, 5386.
22. 5 times more reactive toward nucleophiles than alkyl tosylates, the electrophilicity of 1 lies between methyl triflate and methyl tosylate. (a) Stang, P. J.; Hanack, M.; Subramanian, L. R. Synthesis 1982, 85. (b) Su, T. M.; Sliwinski, W. F.; Schleyer, P. v. R. J. Am. Chem. Soc. 1969, 91, 5386.
23. Casey, C. P.; Brady, J. T.; Boller, T. M.; Weinhold, F.; Hayashi, R. K. J. Am. Chem. Soc. 1998, 120, 12500.
24. The in situ formation of 7 was independently confirmed in a separate experiment by trapping it with trimethylsilyl chloride to form 1 -(trimethylsilyl)-2-phenyl-cyclopropene. See Supporting Information.
25. Similar rearrangements are normally observed at elevated temperatures, although sulfonyl-substituted cyclopropenes undergo ring opening at -25°C. Franck-Neumann, M.; Lohmann, J.-J. Angew. Chem., Int. Ed. Engl. 1977, 16, 323.
26. For a related metal-induced intramolecular cyclization via carbenoid intermediates, see: Shiu, Y.-T.; Madhushaw, R. J.; Li, W.-T.; Lin, Y.-C.; Lee, G.-H.; Peng; S.-M.; Liao, F.-L.; Wang, S.-L.; Liu, R.-S. J. Am. Chem. Soc. 1999, 121, 4066.