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 catalytic cycle.

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 CF(3) 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 its phosphine ligand. An electron-deficient phosphine thwarts the reduction step but, based on the Ru-S catalyst, half of an equivalent of an added alkoxide not only facilitates but also accelerates the catalysis. The intriguing effect is rationalized by the formation of a hydride-bridged Ru-S dimer that was detected by (1)H NMR spectroscopy. A refined catalytic cycle is proposed.