Journal article
In Situ Spectroscopic Investigation of the Rhenium-Catalyzed Deoxydehydration of Vicinal Diols
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.
Language: | English |
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Year: | 2015 |
Pages: | 1184-1196 |
ISSN: | 18673899 and 18673880 |
Types: | Journal article |
DOI: | 10.1002/cctc.201403012 |
ORCIDs: | Fristrup, Peter |