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Photochemically Induced Intramolecular Six‐Electron Reductive Elimination and Oxidative Addition of Nitric Oxide by the Nitridoosmate(VIII) Anion
Author(s) -
Thornley Wyatt A.,
Bitterwolf Thomas E.
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201408816
Subject(s) - intramolecular force , chemistry , nitric oxide , oxidative phosphorylation , ion , electron , oxide , oxidative addition , photochemistry , medicinal chemistry , stereochemistry , organic chemistry , catalysis , biochemistry , physics , quantum mechanics
UV photolysis of the nitridoosmate(VIII) anion, OsO 3 N − , in low‐temperature frozen matrices results in nitrogen–oxygen bond formation to give the Os II nitrosyl complex OsO 2 (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, OsO 2 (η 2 ‐NO) − .