title: Photochemically induced intramolecular six-electron reductive elimination and oxidative addition of nitric oxide by the nitridoosmate(VIII) anion.
abstract: UV photolysis of the nitridoosmate(VIII) anion, OsO3 N(-) , in low-temperature frozen matrices results in nitrogen-oxygen bond formation to give the Os(II) nitrosyl complex OsO2 (NO)(-) . Photolysis of the Os(II) nitrosyl product with visible wavelengths results in reversion to the parent Os(VIII) 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 Os(VI) intermediate, OsO2 (η(2) -NO)(-) .
authors.affiliation: Department of Chemistry, University of Idaho, 875 Perimeter Dr, Moscow, ID 83844-2343 (USA).
authors.forename: Wyatt A
authors.initials: WA
authors.lastname: Thornley
authors.forename: Thomas E
authors.initials: TE
authors.lastname: Bitterwolf
keywords: nitrides; osmium; oxidative addition; photochemistry; reductive elimination