Photochemically Induced Intramolecular Six‐Electron Reductive Elimination and Oxidative Addition of Nitric Oxide by the Nitridoosmate(VIII) Anion

Abstract

AbstractUV photolysis of the nitridoosmate(VIII) anion, OsO3N−, in low‐temperature frozen matrices results in nitrogen–oxygen bond formation to give the OsII nitrosyl complex OsO2(NO)−. Photolysis of the OsII nitrosyl product with visible wavelengths results in reversion to the parent OsVIII complex. Formally a six‐electron reductive elimination and oxidative addition, respectively, this represents the first reported example of such an intramolecular transformation. DFT modelling of this reaction proceeds through a step‐wise mechanism taking place through a side‐on nitroxyl OsVI intermediate, OsO2(η2‐NO)−.