A High-Valent Iron(IV) Peroxo Core Derived from O2.

Dioxygen-tolerant [NiFe] hydrogenases catalyze not only the conversion of H2 into 2H+ and 2e- but also the reduction of O2 to H2O. 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 FROM AUTHOR]