High-valent oxo, methoxorhenium complexes: models for intermediates and transition states in proton-coupled multi-electron transfer reactions

The reaction of trans-dioxorhenium complex with methyl trifluoromethanesulfonate produces high-valent, highly stable oxo-, methoxorhenium complexes. These complexes are identical to analogous oxo, hydroxo complexes of trans-dioxorhenium(V)tetrapyridyl species, which is a model system for interfacial two-electron, two proton transfer reaction sequences. High pH stabilizes the rhenium(IV) state for several complexes with respect to redox disproportionation.