Double Oxidative Addition of Singlet Oxygen to Dinuclear Rh(I) Thiolato Complexes
Ana Gamboa, Dong Zhang, and Matthias Selke
Late transition thiolato complexes are of great interest and importance to study because of their high catalytic activity in hydroformulation[i]. In addition, many dinuculear transition metal complexes that are biologically active do undergo oxidative addition at both metal centers (i.e. double oxidative addition). Examples include the oxygen activation of the following biologically active catalysts: methane monooxygenase, ribonucleotide reductase, and hemocyanin.[ii]. However, according to Bosnich[iii] and Halpern[iv], double oxidative addition reactions at both dinuclear centers in the absence of metal-metal bonds have rarely been observed in a laboratory. Up to date, very little is known about the factors that determine the reactivity of dioxygen with transition metal dinuclear complexes.
In order to better understand the reactivity of such systems, a model dinuclear Rh(I) thiolato complex has been synthesized:
Further studies include competition experiments to determine the rates of oxidation of each of the metal centers, and O-17 NMR to prove the formation of the dinuclear peroxo species.
[i] Galvez, C., Ho, D., Azod, A., Selke, M., J. Am. Chem. Soc., 2001, 123, 3381.
[ii] Farmer, P., Solouki, D., Mills, K., Soma, T., Russell., D, Reibenspes, J., Darensbourge, M., J. Am. Chem. Soc., 1992, 114, 4601.
 (a) Dilworth, J.R.; Morales, D. and Zheng, Y. J. Chem. Soc., Dalton Trans., 2000, 3007
(b) Claver, C.; Kalck, P.; Ridmy, M.; Thorez, A.; Oro, L.A.; Pinillos, M.T.; Apreda, M.C.; Cano, F.H. and Foces-Foces, C. J. Chem. Soc., Dalton Trans., 1988, 1523.
 Ho, David. Reaction of Singlet Oxygen with Organometalllic and Phosphorous Compounds, MS thesis, California State University, Los Angeles, 2001. pp.31.
 (a) McCollum, D.; Yap, G.P.A.; Liable-Sands, L,; Rheingold, A.L.; Bosnich, B. Inor. Chem. 1997, 36, 2230; (b) McCollum, D.; Yap, G.P.A.; Rheingold, A.L.; Bosnich, B. J. Am. Chem. Soc. 1996, 118, 1365; (c) McCollum, D.; Fraser, C.; Ostrander, R.; Rheingold, A.L.; Bosnich, B. Inorg. Chem. 1994, 33, 2383.
 (a) Halpern, J. Inorg. Chim. Acta. 1982, 62, 31; (b) Halpern, J. J. Chem. Soc., Chem. Commun. 1973, 629.
 Galvez, C., Ho, D., Azod, A., Selke, M., J. Am. Chem. Soc., 2001, 123, 3381.
HOME  Farmer, P., Solouki, D., Mills, K., Soma, T., Russell., D, Reibenspes, J., Darensbourge, M., J. Am. Chem. Soc., 1992, 114, 4601.