Nonclassical Carbocations as C−H Hydrogen Bond Donors

Abstract

Computed [B3LYP/6-31+G(d,p) and MP2/6-31+G(d,p)] structures and binding energies for complexes of nonclassical cations (carbonium ions) with ammonia, in the gas phase and several solvents, are described. Overall, nonclassical cations are found to be competent C-H hydrogen bond donors. The potential relevance of the C-H...N interactions holding the carbocation.amine complexes together for enzyme-catalyzed terpenoid synthesis is discussed.