Photochemically Induced Intramolecular Six-Electron Reductive Elimination and Oxidative Addition of Nitric Oxide by the Nitridoosmate(VIII) Anion
Wyatt A. Thornley
Department of Chemistry, University of Idaho, 875 Perimeter Dr, Moscow, ID 83844-2343 (USA)
Search for more papers by this authorCorresponding Author
Dr. Thomas E. Bitterwolf
Department of Chemistry, University of Idaho, 875 Perimeter Dr, Moscow, ID 83844-2343 (USA)
Department of Chemistry, University of Idaho, 875 Perimeter Dr, Moscow, ID 83844-2343 (USA)Search for more papers by this authorWyatt A. Thornley
Department of Chemistry, University of Idaho, 875 Perimeter Dr, Moscow, ID 83844-2343 (USA)
Search for more papers by this authorCorresponding Author
Dr. Thomas E. Bitterwolf
Department of Chemistry, University of Idaho, 875 Perimeter Dr, Moscow, ID 83844-2343 (USA)
Department of Chemistry, University of Idaho, 875 Perimeter Dr, Moscow, ID 83844-2343 (USA)Search for more papers by this authorAbstract
UV 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)−.
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