Reactivity of Rhodium–Triflate Complexes with Diphenylsilane: Evidence for Silylene Intermediacy in Stoichiometric and Catalytic Reactions

R Goikhman, D Milstein

Index: Goikhman, Roman; Milstein, David Chemistry - A European Journal, 2005 , vol. 11, # 10 p. 2983 - 2988

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Citation Number: 38

Abstract

Abstract Addition of Ph 2 SiH 2 to [Rh (iPr 3 P) 2 (OTf)](1) yielded the thermally unstable Rh III adduct [Rh (iPr 3 P) 2 (OTf)(H)(SiPh 2 H)](2), which decomposed to [Rh (iPr 3 P) 2 (H) 2 (OTf)](3), liberating (unobserved) silylene. The silylene was trapped by 1, resulting in the Rh I–silyl complex [Rh (iPr 3 P) 2 (SiPh 2 OTf)]. Complex 3 was converted to 2 by addition of diphenylsilane, providing a basis for a possible catalytic cycle. The last reaction did not ...