C (sp3)–F Bond Activation of CF3-Substituted Anilines with Catalytically Generated Silicon Cations: Spectroscopic Evidence for a Hydride-Bridged Ru–S Dimer in the …

T Stahl, HFT Klare, M Oestreich

Index: Stahl, Timo; Klare, Hendrik F. T.; Oestreich, Martin Journal of the American Chemical Society, 2013 , vol. 135, # 4 p. 1248 - 1251

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Citation Number: 35

Abstract

Heterolytic splitting of the Si–H bond mediated by a Ru–S bond forms a sulfur-stabilized silicon cation that is sufficiently electrophilic to abstract fluoride from CF3 groups attached to selected anilines. The ability of the Ru–H complex, generated in the cooperative activation step, to intramolecularly transfer its hydride to the intermediate carbenium ion (stabilized in the form of a cationic thioether complex) is markedly dependent on the electronic nature of ...