Activationless Electron Self-Exchange of High-Valent Oxo and Imido Complexes of Chromium Corroles.

Inorganic chemistry

PubMedID: 26327522

Liu S, Jung J, Ohkubo K, Hicks SD, Bougher CJ, Abu-Omar MM, Fukuzumi S. Activationless Electron Self-Exchange of High-Valent Oxo and Imido Complexes of Chromium Corroles. Inorg Chem. 2015;.
Rate constants of electron self-exchange of high-valent oxo and imido complexes of chromium(V/IV) corrole have been determined in acetonitrile and toluene at various temperatures by electron paramagnetic resonance (EPR) line width variation of the EPR spectra. The observed activation enthalpies (?Hobs(?)) of electron self-exchange of chromium(V)-oxo and -imido corrole with the corresponding chromium(IV) complexes are zero in toluene, whereas the ?Hobs(?) values are slightly positive in acetonitrile. Such activationless electron self-exchange transfer resulted in extremely fast electron-transfer reactions of chromium(V)-oxo and -imido corrole in sharp contrast with slow electron-transfer reactions of other high-valent metal-oxo and -imido complexes.