The mechanism of the CH3ReO3-catalyzed deoxydehydration of a vicinal diol to an alkene driven by oxidation of a secondary alcohol was investigated by time-resolved, in situ IR spectroscopy and was found to occur in three steps: 1) reduction of the catalytically active methyltrioxorhenium(VII) to a rhenium(V) complex (the rate-limiting step), 2) condensation of the diol and the rhenium(V) complex to a rhenium(V) diolate, and 3) extrusion of the alkene accompanied by oxidation of the Re center and thus regeneration of CH3ReO3. The reaction follows zero-order kinetics initially but, unexpectedly, accelerates towards the end, which is explained in terms of a deactivating pre-equilibrium, in which the catalytically active CH3ReO3 condenses reversibly with the diol to form an inactive rhenium(VII) diolate. This conclusion is supported by the direct observation of a catalytically inactive species as well as DFT calculations of the IR spectra of the relevant compounds.
Dethlefsen, J. R., & Fristrup, P. (2015). In Situ Spectroscopic Investigation of the Rhenium-Catalyzed Deoxydehydration of Vicinal Diols. ChemCatChem, 7(7), 1184-1196. https://doi.org/10.1002/cctc.201403012