Kinetics and Mechanism of the Reactions of Amine Boranes with Carbenium Ions

The kinetics of the reactions of trialkylamine boranes and pyridine boranes with benzhydryl cations have been determined photometrically. Second‐order rate laws are obeyed, first‐order with respect to amine borane concentration and first‐order with respect to carbocation concentration. As for other reactions of carbocations with neutral nucleophiles, the rates of these reactions are only slightly affected by solvent polarity. The structure—reactivity relationships and kinetic isotope effects are in accord with a polar mechanism proceeding through a transition state where the migrating hydride is partly bound to the entering carbon and to the leaving boron atom. The rate constants correlate linearly with the electrophilicity parameters E of the carbenium ions. It is therefore possible to use the linear free enthalpy relationship logk2 = s(E+N) for determining nucleophilicity parameters N for the amine boranes and to compare their hydride‐donating abilities with those of other non‐charged hydride donors (silanes, germanes, stannanes, and dihydropyridines).