A High‐Valent Iron(IV) Peroxo Core Derived from O2. Issue 2 (28th October 2015)

• Record Type: Journal Article
• Authors: Kishima, Takahiro; Matsumoto, Takahiro; Nakai, Hidetaka; Hayami, Shinya; Ohta, Takehiro; Ogo, Seiji
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 2(2016)
• Page Start: 724
• Page End: 727
• Publication Date: 2015-10-28
• Subjects: dioxygen ligands -- hydrogenases -- iron -- peroxo complexes; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201507022
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Dioxygen‐tolerant [NiFe] hydrogenases catalyze not only the conversion of H2 into 2 H + and 2 e − but also the reduction of O2 to H2 O. Chemists have sought to mimic such bifunctional catalysts with structurally simpler compounds to facilitate analysis and improvement. Herein, we report a new [NiFe]‐based catalyst for O2 reduction via an O2 adduct. Structural investigations reveal the first example of a side‐on iron(IV) peroxo complex. Abstract : Dioxygen‐tolerant [NiFe] hydrogenases catalyze not only the conversion of H2 into 2 H + and 2 e − but also the reduction of O2 to H2 O. A new [NiFe]‐based complex is a synthetic mimic of such hydrogenases and catalyzes O2 reduction via an O2 adduct, which was shown to be the first example of a side‐on iron(IV) peroxo complex.