title: Correlation of the Rates of Solvolysis of the Benzhydryldimethylsulfonium Ion. Application of the Aromatic Ring Parameter(1).
abstract: Values for the specific rates of solvolysis of the benzhydryldimethylsulfonium ion in 34 solvents have been analyzed using various forms of the extended Grunwald-Winstein equation. The specific rates are insensitive toward changes in solvent nucleophilicity (N(T)) values, and they correlate best against a combination of Y(+) values (based on the solvolyses of the 1-adamantyldimethylsulfonium ion) and aromatic ring parameter (I) values. Common-molecule return is observed, being especially powerful in solvents rich in fluoro alcohol; the logarithm of the associated mass law constant correlates inversely with the solvent N(T) values. The product selectivities in ethanol-water mixtures are also consistent with an S(N)1 mechanism for the solvolyses.
authors.affiliation: Department of Chemistry, Northern Illinois University, DeKalb, Illinois 60115-2862.
authors.forename: Dennis N.
authors.initials: DN
authors.lastname: Kevill
authors.forename: Steven W.
authors.initials: SW
authors.lastname: Anderson
authors.forename: Norsaadah HJ
authors.initials: NH
authors.lastname: Ismail