Kinetic and mechanistic studies of a regioselective, rhenium-catalyzed monoalkylation of phenols has revealed a reaction mechanism which is zeroth order with respect to both alkene and phenol species, and fractional order relative to the addition of rhenium catalyst. This observed fractional order is indicative of a mechanism featuring some form of catalyst deaggregation from a precatalytic complex to a catalytically operative monomeric species. The complexity of the precatalytic complex makes it likely that deaggregation occurs via a series of intermediate steps, which include asymmetric bond cleavage and solvent coordination. In this work, we make use of electronic structure methods, including one-dimensional scans, in order to evaluate potential intermediates in the deaggregation process and locate transition state structures for the interconversion between intermediates. The results shed light on the probable structure of the precatalytic complex and provide insight into the rate determining step for this reaction.

Investigation of the rate-determining deaggregation step in a rhenium-catalyzed monoalkylation of phenols

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