Nucleophilic displacement on 4-nitrophenyl dimethyl phosphinate by ethoxide ion: alkali metal ion catalysis and mechanism.

We report on a spectrophotometric kinetic study of the effect of Li(+) and K(+) cations on the ethanolysis of 4-nitrophenyl dimethylphosphinate () in ethanol at 25 [degree]C. The nucleophilic displacement reaction of with LiOEt and KOEt in the absence and presence of 18-crown-6 ether (18-C-6) furnished observed first-order rate constants which increase in the order EtO(-) < KOEt < LiOEt. The kinetic data are analyzed in terms of a scheme which assigns concurrent kinetic activity to free ethoxide and metal alkoxide, to obtain the second-order rate coefficients for reaction of the metal ion-ethoxide pairs, k(MOEt). Derived [small delta]G(ip), [small delta]G(ts) and [capital Delta]G(cat) values quantify ground state and transition state stabilization by the metal ions to give [small delta]G(ts) > [small delta]G(ip) for Li(+) and [small delta]G(ts)[similar][small delta]G(ip) for K(+). These results indicate moderate catalysis by Li(+), with manifesting lesser susceptibility to catalysis than other substrates previously studied. Second-order rate constants for the reaction of the aryl dimethylphosphinates with free EtO(-) were obtained from plots of log k(obs)vs. [KOEt], measured in the presence of excess 18-C-6. Hammett plots with [sigma] and [sigma][degree] substituent constants give significantly better correlation of rates than sigma and yield a moderately large [small rho]([small rho][degree]) value; this is interpreted in terms of a stepwise mechanism involving rate-limiting formation of a pentacoordinate intermediate. Comparison of the present results with those of Williams on the aqueous alkaline hydrolysis of Me(2)P(O)-OPhX and Ph(2)P(O)-OPhX esters, establishes the rationale for a change in mechanism in the more basic EtO(-)/EtOH nucleophile/solvent system by a stepwise mechanism instead of a concerted one in aqueous base. Structure-reactivity correlations following Jencks show that the change in mechanism is accounted for by cross interactions between the nucleophile and the leaving group in the transition state. The observed duality of mechanism is rationalized on the basis of the More O'Ferrall-Jencks diagram, as a spectrum of transition states covering a wide range of nucleophile and leaving group basicities.