Formation and redox reactivity of osmium(II) thionitrosyl complexes

Thionitrosyl complexes, together with -SCN and N2, were produced from the 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. Analysis shows that such complexes exhibit versatile and extensive redox chemistry in [OsII(tpm)(Cl)2(NS)]+. The ability of the NS group to move a S atom to PPh3 was revealed by the reaction between [OsII(tpm)(Cl)(NS)]+ (3b) and PPh3(eq 3).