A high-valent trans-[Ru(TMC)O2]2+ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) cation has been produced from trans-[Ru(TMC)Cl2]+ through H2O2 oxidation. This novel diamagnetic ruthenium(VI) dioxo species has been subjected to detailed spectroscopic and electrochemical characterization. The UV-vis absorption spectra of trans-[Ru(TMC)O2]2+ and the previously reported trans-[Ru(NH3)4O2]2+ exhibit a weak vibronic structured absorption band at ∼390 nm. Cyclic voltammetric and controlled-potential coulometric experiments showed that the reduction of trans-[Ru(TMC)O2]2+ to trans-[Ru(TMC)O-(H2O)]2+ proceeded by a single-step two-electron-transfer process.
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Che et al. (1985) studied this question.