Conversion of Molecular Oxygen into a Hydroperoxo Species by Ring-Opening Protonation of a Cyclic eta(2)-Peroxo Intermediate: Characterization of the eta(2)-Peroxo and Hydroperoxo Complexes.

Abstract

A transition metal-hydroperoxo species is formed by the oxygenation of a low-valent rhodium precursor followed by a protonation of the resulting eta(2)-O(2) ligand; the latter process is assisted by an intramolecular hydrogen-bonding interaction (see scheme). This process is the first structural evidence for an effective method for the activation of molecular oxygen as postulated for the cytochrome P-450 system.