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Grapperhaus, C.A. et al.

Grapperhaus, Poturovic, Mashuta,

Oxygenation of a ruthenium(II) thiolate to a ruthenium(II) sulfinate proceeds via ruthenium(III).

Exposure of acetonitrile/methanol solutions of [PPN][Ru(DPPBT)3] [ PPN = bis(triphenylphosphoranylidene); DPPBT = 2-diphenylphosphinobenzene thiolate] to oxygen initiates metal-centered oxidation, yielding the ruthenium(III) thiolate Ru(DPPBT)3. Ru(DPPBT)3 further reacts with oxygen, at sulfur, to give the ruthenium(III) sulfinate complex [Ru(DPPBT-O2)2(DPPBT)], which is reduced under ambient conditions to [PPN][Ru(DPPBT-O2)2(DPPBT)]. Ruthenium(II) sulfinate is the only product isolated from acetonitrile/methanol. Yellow crystals of [PPN][Ru(DPPBT-O2)2(DPPBT)] were obtained. Ruthenium(III) sulfinate was isolated as green prism-shaped crystals upon oxygenation of [PPN][Ru(DPPBT)3] in chlorobenzene/hexane. Electrochemical oxidation of ruthenium(II) sulfinate yields the ruthenium(III) derivative, which is rapidly reduced back to ruthenium(II) upon the addition of hydroxide.[1]

References

Oxygenation of a ruthenium(II) thiolate to a ruthenium(II) sulfinate proceeds via ruthenium(III). Grapperhaus, C.A., Poturovic, S., Mashuta, M.S. Inorganic chemistry. (2005) [Pubmed]

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