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 (1 > 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 & Aring;, respectively.

Automated summary

Upon irradiation by blue LED (>460 nm), tricyano osmium nitrido complex [Os-VI(N)(L)(CN)(3)]- (OsN) can abstract chalcogen atoms from anions NCE- (E = O, S, Se) to form metal chalcogenonitrosyls [Os-II(NuE)(L)(CN)(3)]- (OsNE) and CN-. The photoreaction of OsN with organic sulfide, such as diisopropyl sulfide, also results in S atom abstraction and the formation of OsNS and Os-NvC(CH3)(2). The X-ray crystallographic study reveals the N-O, N-S, and N-Se bond distances of 1.206, 1.507, and 1.675 Å in (PPh4)[Os-II(NuE)(L)(CN)(3)].