Methylrhenium trioxide (MTO) has the rare ability to stoichiometrically generate methanol at room temperature with an external oxidant (H2O2) under basic conditions. In order to use this transformation as a model for nonredox oxidative C-O coupling, the mechanisms have been elucidated using density functional theory (DFT). Our studies show several possible reaction pathways to form methanol, with the lowest net barrier (Delta H-double dagger) being 23.3 kcal mol(-1). The rate-determining step is a direct "Baeyer-Villiger" type concerted oxygen insertion into MTO, forming methoxyrhenium trioxide. The key to the low-energy transition state is the donation of electron density, first, from HOO(-) to the -CH3 group (making -CH3 more nucleophilic and HOO- more electrophilic) and, second, from the Re-C bond to both the forming Re-O and breaking O-O bonds, simultaneously (thus forming the Re-O bond as the Re-C bond is broken). In turn, the ability of MTO to undergo these transfers can be traced to the electrophilic nature of the metal center and to the absence of accessible d-orbitals. If accessible cl-orbitals are present, they would most likely donate the required electron density instead of the M-CH3 moiety, and this bond would thus not be broken. It is possible that other metal centers with similar qualities, such as Pt-IV or Ir-V, could be competent for the same type of chemistry.