Mechanistic Insight into Concerted Proton-Electron Transfer of a Ru(IV)-Oxo Complex: A Possible Oxidative Asynchronicity

We have thoroughly investigated the oxidation of benzyl alcohol (BA) derivatives by a Ru-IV(O) complex (Ru-IV(O)) in the absence or presence of Brmnsted acids in order to elucidate the proton-coupled electron-transfer (PCET) mechanisms in C-H oxidation on the basis of a kinetic analysis. Oxidation of BA derivatives by Ru-IV(O) without acids proceeded through concerted proton-electron transfer (CPET) with a large kinetic isotope effect (KIE). In contrast, the oxidation of 3,4,5-trimethoxyBA ((MeO)(3)-BA) by Ru-IV(O) was accelerated by the addition of acids, in which the KIE value reached 1.1 with TFA (SSO mM), indicating an alteration of the PCET mechanism from CPET to stepwise electron transfer (ET) followed by proton transfer (PT). Although the oxidized products of BA derivatives were confirmed to be the corresponding benzaldehydes in the range of acid concentrations (0-550 mM), a one-electron-reduction potential of Ru-IV(O) was positively shifted with increases in the concentrations of acids. The elevated reduction potential of Ru-IV(O) strongly influenced the PCET mechanisms in the oxidation of (MeO)(3)-BA, changing the mechanism from CPET to ET/PT, as evidenced by the driving-force dependence of logarithms of reaction rate constants in light of the Marcus theory of ET. In addition, dependence of activation parameters on acid concentrations suggested that an oxidative asynchronous CPET, which is not an admixture of the CPET and ET/PT mechanisms, is probably operative in the boundary region (0 mM < [TFA] < SO mM) involving a one-protoninteracted Ru-IV(O)center dot center dot center dot H+ as a dominant reactive species.