J Phys Chem A. 2013 Oct 10;117(40):10551-62. doi: 10.1021/jp4081788. Epub 2013 Sep 25.
The journal of physical chemistry. A
Upendra Adhikari, Steve Scheiner
PMID: 24028630 DOI: 10.1021/jp4081788
Quantum calculations find that neutral methylamines and thioethers form complexes, with N-methylacetamide (NMA) as proton acceptor, with binding energies of 2-5 kcal/mol. This interaction is magnified by a factor of 4-9, bringing the binding energy up to as much as 20 kcal/mol, when a CH3(+) group is added to the proton donor. Complexes prefer trifurcated arrangements, wherein three separate methyl groups donate a proton to the O acceptor. Binding energies lessen when the systems are immersed in solvents of increasing polarity, but the ionic complexes retain their favored status even in water. The binding energy is reduced when the methyl groups are replaced by longer alkyl chains. The proton acceptor prefers to associate with those CH groups that are as close as possible to the S/N center of the formal positive charge. A single linear CH··O hydrogen bond (H-bond) is less favorable than is trifurcation with three separate methyl groups. A trifurcated arrangement with three H atoms of the same methyl group is even less favorable. Various means of analysis, including NBO, SAPT, NMR, and electron density shifts, all identify the (+)CH··O interaction as a true H-bond.
