Chalcogen atom abstraction from NCE^- (E = O, S, Se) and i-Pr₂S by the excited state of a luminescent tricyano osmium(VI) nitride

Upon irradiation by blue LED (lambda > 460 nm), the tricyano osmium nitrido complex [Os-VI(N)(L)(CN)(3)](-) (OsN) in its excited state readily abstracts chalcogen atoms from the anions NCE- (E = O, S, Se) to give the corresponding metal chalcogenonitrosyls [Os-II(NuE)(L)(CN)(3)](-) (OsNE) and CN-. A similar S atom abstraction also occurs in the photoreaction of OsN with organic sulfide, such as diisopropyl sulfide, to give OsNS and Os-NvC(CH3)(2). The molecular structures of (PPh4)[Os-II(NuE)(L)(CN)(3)] have been determined by X-ray crystallography, which show N-O, N-S and N-Se bond distances of 1.206, 1.507 and 1.675 angstrom, respectively.