The nucleophilicity of biomimetic zinc-thiolate complexes against methyl iodide has been studied. The activation barrier has been computed with the B3LYP functional. The reactivity depends on the global charge, the nature of the ligand set and the presence of hydrogen bonds. This shows that the understanding of zinc site nucleophilicity can not be achieved by the knowledge of the atom donor set...

This work deals with exploring some empirical scales of nucleophilicity. We have started evaluating the experimental indices of nucleophilicity proposed by Legon and Millen on the basis of the measure of the force constants derived from vibrational frequencies using a probe dipole H-X (X = F,CN). The correlation among some theoretical parameters with this experimental scale has been evaluated. ...

The paths of nucleophilic fluoroalkylation reaction of propylene oxide with PhSO2CYF (Y = F, H, and PhSO2, respectively) in the gas phase and in Et2O solvent were studied theoretically. The nucleophilic fluoroalkylation of propylene oxide with fluorinated carbanions was probed by comparison of the reactivities (phenylsulfonyl)monofluoromethyl anion (PhSO2CHF), the (phenylsulfonyl)difluoromethyl...

The adjacent centres of electrophilicity and nucleophilicity lead to interesting chemical reactivity in the title reagent.

The specific rates of solvolysis of S-methyl chlorothioformate (MeSCOCl) are analyzed in 20 solvents of widely varying nucleophilicity and ionizing power at 25.0 degrees C using the extended Grunwald-Winstein Equation. A stepwise S(N)1 (D(N) + A(N)) mechanism is proposed in the more ionizing solvents including six aqueous fluoroalcohols. In these solvents, a large sensitivity value of 0.79 towa...

A set of model nucleophiles of gradually changing nucleophilicity is used to probe the glycosylation reaction mechanism. Glycosylations of ethanol-based acceptors, bearing varying amounts of fluorine atoms, report on the dependency of the stereochemistry in condensation reactions on the nucleophilicity of the acceptor. Three different glycosylation systems were scrutinized, that differ in the r...