39014-36-3Relevant academic research and scientific papers
Oxonium Ions. Solvation by Single Acetonitrile Molecules in the Gas Phase and by Bulk Solvents
Bromilow, J.,Abboud, J. L. M.,Lebrilla, C. B.,Taft, R. W.,Scorrano, G.,Lucchini V.
, p. 5448 - 5453 (2007/10/02)
The standard free energy of formation of gaseous complexes between monoprotonic oxonium ions and acetonitrile have been obtained by using the ion cyclotron resonance equilibrium constant method for exchange of acetonitrile between the ions.The results show that the "solvation" by a single molecule of acetonitrile in the gas phase reproduces the important diverse effects of molecular structure on oxonium ion solvation by bulk water.It is estimated from the present results that the effects of solvation by bulk water are only about three times as great as the corresponding effects of "solvation" by a single water molecule in the gas phase.Internal charge delocalization from the protonic site of the oxonium ions may be reversed by differential solvation, both with single H-bonding molecules in the gas phase and with bulk solvent.Further evidence for the site of preffered protonation of esters and amides is provided.
Proton Affinities and Photoelectron Spectra of Three-Membered-Ring Heterocycles
Aue, Donald H.,Webb, Hugh M.,Davidson, William R.,Vidal, Mariano,Bowers, Michael T.,at al.
, p. 5151 - 5157 (2007/10/02)
Proton affinities and photoelectron spectra have been measured for azirane, phosphorane, oxirane, and thiirane and for the corresponding dimethylamine, phosphine, ether, and sulphide.The photoelectron spectra have been fully assigned by the use of ab initio STO-431G calculations and structural correlations within these series of molecules.The lone-pair ionization potentials of the heterocycles are higher than those of their open-chain dimethyl analogues because of charge redistribution effects in the C-X bonds and increased lone-pair's character in azirane and phosphirane.The proton affinities are lower in the heterocycles than in their dimethyl analogues as a result of increases in lone-pair's character and, especially for phosphirane, an increase in the RXR angle strain on protonation.Ab initio calculations on the protonated heterocycles and XHn models are presented to help interpret the proton-affinity data.
