Formation and Redox Reactivity of Osmium(II) Thionitrosyl Complexes

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Abstract

Reaction between [Os(VI)(tpm)(Cl)(2)(N)](PF(6)) (tpm = tris(1-pyrazolyl)methane) (1) or Os(VI)(Tp)(Cl)(2)(N) (Tp = hydrotris(1-pyrazolyl)borate anion) (2) and CS(2) + N(3)(-) in acetone gives the corresponding thionitrosyl complexes, (-)SCN, and N(2). There is an extensive reactivity chemistry of the thionitrosyl group in [Os(II)(tpm)(Cl)(2)(NS)](PF(6)) (3b). Reaction between 3b and PPh(3) occurs with S-atom transfer to give [Os(IV)(tpm)(Cl)(2)(NPPh(3))](+) and S=PPh(3). 3b undergoes chemical or electrochemical reduction to give the corresponding Os(II) ammine complex and H(2)S. O-atom transfer from O=NMe(3) to 3b occurs to give Os(III)(tpm)(Cl)(2)(NSO). Competitive NO(+)/NS(+) exchange and S(2)(-) transfer occur in the reaction between [Os(II)(tpm)(Cl)(2)(NS)](BF(4)) (3c) and NO(+) to give a mixture of [Os(VI)(tpm)(Cl)(2)(N)](+) and [Os(II)(tpm)(Cl)(2)(NO)](+).

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