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

Thornley Wyatt A. | Zendy; Bitterwolf Thomas E. | Zendy

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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) − .

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