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Formation and Redox Reactivity of Osmium(II) Thionitrosyl Complexes

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posted on 1999-06-16, 00:00 authored by El-Sayed El-Samanody, Konstantinos D. Demadis, Laurie A. Gallagher, Thomas J. Meyer, Peter S. White
Reaction between [OsVI(tpm)(Cl)2(N)](PF6) (tpm = tris(1-pyrazolyl)methane) (1) or OsVI(Tp)(Cl)2(N) (Tp = hydrotris(1-pyrazolyl)borate anion) (2) and CS2 + N3- in acetone gives the corresponding thionitrosyl complexes, -SCN, and N2. There is an extensive reactivity chemistry of the thionitrosyl group in [OsII(tpm)(Cl)2(NS)](PF6) (3b). Reaction between 3b and PPh3 occurs with S-atom transfer to give [OsIV(tpm)(Cl)2(NPPh3)]+ and SPPh3. 3b undergoes chemical or electrochemical reduction to give the corresponding OsII ammine complex and H2S. O-atom transfer from ONMe3 to 3b occurs to give OsIII(tpm)(Cl)2(NSO). Competitive NO+/NS+ exchange and S2- transfer occur in the reaction between [OsII(tpm)(Cl)2(NS)](BF4) (3c) and NO+ to give a mixture of [OsVI(tpm)(Cl)2(N)]+ and [OsII(tpm)(Cl)2(NO)]+.

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