"Redox-Switch" Catalysis of C-C Bond Formation with H2: One-Electron Reduction of the Trityl Cation

Angewandte Chemie (International Edition in English)

Volumn 36, Issue 1-2, 1997, Pages 65-67

  Membre, Robert T ^a,b   McQueen, J Scott ^a  

^a UNIVERSITY OF NEBRASKA LINCOLN   (United States)

^b EASTMAN CHEMICAL COMPANY   (United States)

Author keywords

Catalysis; Reductions; Ruthenium; Trityl cation

Indexed keywords

EID: 0030797581     PISSN: 05700833     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.199700651     Document Type: Article

References (28)

1. +[2], Little elaboration on this seminal work has been reported in the extensive development of hydrogenation catalysis during the intervening three and a half decades.
2. J. Halpern, Q. Rev. Chem. Soc. 1956, 10, 463-479; S. Ciccone, J. Halpern, J. F. Harrod, Can. J. Chem. 1961, 39, 1372-1376.
3. J. Halpern, Q. Rev. Chem. Soc. 1956, 10, 463-479; S. Ciccone, J. Halpern, J. F. Harrod, Can. J. Chem. 1961, 39, 1372-1376.
4. R. T. Membre, J. S. McQueen, V. W. Day, J. Am. Chem. Soc. 1996, 118, 798-803.
5. J. M. McBride, Tetrahedron 1974, 30, 2009-2022.
6. 3CH by an eH mechanism. Thus, an eH hydride transfer can yield products in relative amounts that depend on the ratio of the trityl cation to the metal hydride. We have reported such variations in the reaction of [Cp*(dppm)RuH] with the trityl cation (dppm = bisdiphenylphosphinomcthane) [7]. The products of a single-step hydride transfer are, on the other hand, insensitive to this ratio.
7. O. B. Ryan, M. Tilset, V. D. Parker, Organometatlics 1991, 10, 298-304.
8. R. T. Hembre, J. S. McQueen, J. Am. Chem. Soc. 1994, 116, 2141-2142.
9. The trityl radical is in equilibrium with Gomberg's dimer at room temperature : W. P, Neumann, W Uzick, A. Zarkadis, J. Am. Chem. Soc. 1986, 108, 3762-3770.
10. 3C, derived from Gomberg's dimer [8] is an effective H-atom abstractor from certain metal hydrides: D. C. Eisenberg, J. R. Norton, Isr. J. Chem. 1991, 31, 55-66.
11. DMSO = + 0.280 V): J. Cheng, K. L. Handoo, V. D. Parker, J. Am. Chem. Soc. 1993. 115, 2655-2660.
12. While oxidation of transition metal hydrides by electron transfer is well known [12] (including such oxidation by the trityl cation), [13] we are aware of no precedent for an eH hydride transfer.
13. O. B. Ryan, M. Tilset, V. D. Parker. J. Am. Chem. Soc. 1990, 112, 2618-2626, and references therein.
14. M. Gargano, P. Giannoccaro, M, Rossi, G. Vasapollo, A. Sacco, J. Chem. Soc. Dalton Trans. 1975, 9-12; J. R, Sanders, ibid. 1975, 2340-2342; D. E. Westerberg, L. F. Rhodes, J. Edwin, W. E. Geiger, K. G. Caulton, Inorg. Chem. 1991, 30, 1107-1112.
15. M. Gargano, P. Giannoccaro, M, Rossi, G. Vasapollo, A. Sacco, J. Chem. Soc. Dalton Trans. 1975, 9-12; J. R, Sanders, ibid. 1975, 2340-2342; D. E. Westerberg, L. F. Rhodes, J. Edwin, W. E. Geiger, K. G. Caulton, Inorg. Chem. 1991, 30, 1107-1112.
16. M. Gargano, P. Giannoccaro, M, Rossi, G. Vasapollo, A. Sacco, J. Chem. Soc. Dalton Trans. 1975, 9-12; J. R, Sanders, ibid. 1975, 2340-2342; D. E. Westerberg, L. F. Rhodes, J. Edwin, W. E. Geiger, K. G. Caulton, Inorg. Chem. 1991, 30, 1107-1112.
17. - by Creutz and Bullock [16].
18. W. S. Striejewske, R. F. See, M. R. Churchill, J. D. Atwood, Organometallics 1993, 12, 4413-4419.
19. C. L. Schwarz, R. M. Bullock, C, Creutz, J. Am. Chem. Soc. 1991, 113, 1225-1236.
20. 10] [18].
21. J. R. Pugh, T. J. Meyer, J. Am. Chem. Soc. 1992, 114, 3784-3792.
22. 6) = 3.70, 3.82, 4.09, and 4.65).
23. K. -S. Gan, T. S. A. Hor, in Ferrocenes (Eds: A. Togni, T. Hayashi), VCH, Weinheim, 1995; pp. 3-104.
24. G. Jia, R. H. Morris, J. Am. Chem. Soc. 1991, 113, 175-883.
25. T. M. Miller, K. J. Ahmed, M. S. Wrighton, Inorg. Chem. 1989, 28, 2347-2355.
26. 2Co) = - 0.600 V vs. NHE).
27. P. Zanello, in Ferrocenes (Eas: A. Togni, T. Hayashi), VCH, Weinheim, 1995; pp. 317-425.
28. +.