title: Oxygenation of a ruthenium(II) thiolate to a ruthenium(II) sulfinate proceeds via ruthenium(III).
abstract: 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.
authors.affiliation: Department of Chemistry, University of Louisville, Louisville, Kentucky 40292, USA. grapperhaus@louisville.edu
authors.forename: Craig A
authors.initials: CA
authors.lastname: Grapperhaus
authors.forename: Selma
authors.initials: S
authors.lastname: Poturovic
authors.forename: Mark S
authors.initials: MS
authors.lastname: Mashuta