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

Abstract

Upon irradiation by blue LED (λ > 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(NE)(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–NC(CH₃)₂. The molecular structures of (PPh₄)[Os^II(NE)(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 Å, respectively.