Nonclassical Carbocations as C−H Hydrogen Bond Donors

2006-04-13T00:00:00Z (GMT) by Mihaela D. Bojin Dean J. Tantillo
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.