[MoO2]2+ -Mediated oxygen atom transfer via an unusual lewis acid mechanism

Abstract

Density functional theory is applied to the study of theoxygen atom transfer reaction from sulfoxide (DMSO) to phosphine(PMe 3) catalyzed by the [MoO2]2+ active core. In this work, two fundamentally different roles are explored for this dioxometal complex inthe first step of the catalytic cycle: as an oxidizing agent and as a Lewisacid. The latter turns out to be the favored pathway for the oxygen atomtransfer. This finding may have more general implications for similarreactions catalyzed by the same [MoO2]2+ core.