title: The mechanism of permanganate oxidation of sulfides and sulfoxides.
abstract: Coupled-cluster (CCSD) and density functional computations are used to investigate historically competing mechanisms for the permanganate oxidation of sulfides and sulfoxides. The calculations all lead to a mechanism of 1,3-dipolar cycloaddition of permanganate, as opposed to historical mechanisms of attack of the sulfur atom by one O or by Mn. Such a mechanism, reminiscent of ozonolysis, may prevail in most permanganate oxidations. The ab initio activation enthalpies are in reasonable agreement with the experimental data; the ab initio activation entropies are not, possibly because of problems with Eyring equation assumptions.
authors.affiliation: Department of Chemistry and Biochemistry, University of Regina, Regina, SK S4S 0A2 Canada.
authors.forename: Arumugam
authors.initials: A
authors.lastname: Jayaraman
authors.forename: Allan L L
authors.initials: AL
authors.lastname: East