Nonclassical carbocations as C-H hydrogen bond donors.
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.
Bojin
Mihaela D
MD
Department of Chemistry, University of California, Davis, One Shields Avenue, 95616, USA.
Tantillo
Dean J
DJ
D000641:Ammonia / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry*; D003198:Computer Simulation; D006639:Histidine / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry*; D006860:Hydrogen Bonding; D008239:Lysine / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry
D012997:Solvents; D006639:Histidine; D002244:Carbon; D000641:Ammonia; D006859:Hydrogen; D008239:Lysine