Multiple bonds between main-group elements and transition metals. Part 133. Methyltrioxorhenium as a catalyst of the Baeyer-Villiger oxidation

Abstract

Methyltrioxorhenium CH₃ReO₃ (MTO, 1) is one of the most active catalysts of the Baeyer-Villiger oxidation of cyclic ketones by use of H₂O₂ as oxidant. In contrast to the chemistry of established molybdenum and tungsten peroxo complexes, the bis(peroxo) complex [CH₃ReO(O₂)₂·H₂O] reacts stoichiometrically with ketones. The electronic character of the active species was determined by spectroscopy and by application of an oxygen transfer probe.