title: Characterization of the nucleophilic reactivities of thiocarboxylate, dithiocarbonate and dithiocarbamate anions.
abstract: The kinetics of the reactions of thiocarboxylate and thiocarbonate anions with benzhydrylium ions have been determined in acetonitrile solution using laser-flash photolytic techniques. The second-order rate constants (k) correlate linearly with the electrophilicity parameters E of the benzhydrylium ions, as required by the correlation log k (20 °C) = s(N)(N + E) (J. Am. Chem. Soc., 2001, 123, 9500-9512), allowing us to calculate the nucleophile-specific parameters N and s(N) for these anions. With these parameters, a direct comparison of the reactivities of thiocarboxylate, dithiocarbonate and dithiocarbamate anions with other nucleophiles becomes possible.
authors: Department of Applied Chemistry, Faculty of Science, Xi'an Jiaotong University, Xi'an, 710049, Peoples Republic China.
authors: Xin-Hua
authors: XH
authors: Duan
authors: Biplab
authors: B
authors: Maji
authors: Herbert
authors: H
authors: Mayr