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 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

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... ct comparison of the reactivities of thiocarboxylate, dithiocarbonate and dithiocarbamate anions with other nucleophiles becomes possible. † Electronic supplementary information (ESI) available: Synthetic procedures and product characterization, details of the determination of rate constants. See Structure reactivity relationships Benzhydrylium ion (lil) 2 CH + , the least reactive electrophile of this series, will now be employed to investigate structure reactivity relationships. This journal is