The 4,4'-dimethoxytrityl carbenium ion by ionization of 4,4'-dimethoxytrityl alcohol in acetonitrile - aqueous perchloric and nitric acids containing electrolytes: kinetics, equilibria, and ion-pair formation

Abstract

We have studied the equilibration shown in eq. [3] of 4,4prime-dimethoxytrityl alcohol in aqueous perchloric and nitric acids containing low proportions of acetonitrile using stopped-flow kinetics techniques. The rate constants for the overall progress to equilibrium, kobs, have been resolved into forward and reverse components using the equilibrium UV absorbance and a value for the molar absorptivity of the 4,4prime-dimethoxytrityl carbenium ion determined in concentrated aqueous perchloric acid. The forward reaction (rate constant kf) is first order in both the alcohol and the acid concentrations; the reverse reaction (rate constant kr) is pseudo first order with respect to the carbocation. At constant hydronium ion concentration, the forward rate constant increases linearly with the concentration of electrolyte, whereas the reverse rate constant decreases. These effects depend upon the nature of the anion, but not the cation, and are not ionic strength effects. At constant anion concentrations, kf in both acids, and kr in perchloric acid, are independent of hydronium ion concentration; however, kr decreases with increasing hydronium ion concentration at constant nitrate concentration. At nonconstant ionic strength, changes in kf and kr observed in increasing concentrations of perchloric acid are attributable wholly to changes in perchlorate concentration. A mechanism is proposed which involves pre-equilibrium protonation of the alcohol, heterolysis of the protonated alcohol to give a 4,4prime-dimethoxytrityl carbenium ion - water ion-molecule pair, then conversion of this into a dissociated carbenium ion in equilibrium with ion pairs. To account for the strong effects of perchlorate and nitrate upon the forward rate constants, it is proposed that these anions provide additional reaction channels from the ion-molecule pair. However, we find no evidence of acid catalysis in the reaction of the ion-molecule pair (in contrast to our finding for the reaction of the corresponding ion-molecule pair formed from dimethoxytritylamine in acidic media). Some of the elementary rate and equilibrium constants of the proposed mechanism have been evaluated.Key words: trityl, carbenium ion, stopped-flow, ion pair, ion-molecule pair.