Theoretical study of the solvent effect on the methyltrioxorhenium/hydrogen peroxide system

Abstract

The effect of solvent on the stability and reactivity of methyltrioxorhenium (MTO) for activation of hydrogen peroxide (H 2O2) was investigated theoretically. The possible geometries for all Re complexes present in this system, MTO, monoperoxo complexes [A: MeReO2(η 2-O2) and A·H 2 O: MeReO2(η 2-O2)(H 2O)], and bisperxo complexes [B: MeReO(η 2-O 2)2 and B·H 2 O: MeReO(η 2-O2)2(H2O)] were calculated. Based on the theoretical calculations, species A lacks coordinated water while species B·H 2 O definitely has water coordinated to the Re. The changes of thermodynamic parameters (ΔH and ΔG) for six reactions in the MTO/H2O2, system including formation of mono- and bisperoxo complexes, were determined. © 2013 Springer Science+Business Media New York.