Specific Features of Solvation Effects in Monomolecular and Bimolecular Solvolysis

摘要

A method was suggested for distinguishing monomolecular and bimolecular solvolysis on the basis of reaction inetics in water, MeOH,EtOH,I-PrOH, cyclohexanol, and t-BuOH. In solvolysis of n-PrBr,CH_2 = CHCH_2Br,PhCOCl,and MeOClO_3(Sn2 reactions), a linear correlation is observed between log #kappa# and the solvent ionizing power Z, whereas in solvolysis of t-BuBr,t-BuCl,and 1-AdI (S_N1,E1 reactions) this correlation is nonlinear. Deviations from linearity are due to steric hindrance decreasing the negative effect of nucleophilic solvation.