Characterization of the nucleophilic reactivities of thiocarboxylate, dithiocarbonate and dithiocarbamate anions

Xin-Hua Duan, Biplab Maji, Herbert Mayr
2011 Organic and biomolecular chemistry  
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
more » ... 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
doi:10.1039/c1ob06245j pmid:21975968 fatcat:3dysqip6vvgqnf2zvqg2wd4xsi