Gas-phase basicities of polyfunctional molecules. Part 1: Theory and methods

摘要: The experimental and theoretical methods of determination gas-phase basicities, proton affinities protonation entropies are presented in a tutorial form. Particularities limitations these when applied to polyfunctional molecules emphasized. Structural effects during the process their consequences on corresponding thermochemistry reviewed classified. role nature basic site (protonation non-bonded electron pairs or π-electron systems) substituent (electrostatic resonance) first examined. Then, linear correlations observed between basicities ionization energies constants recalled. Hydrogen bonding plays special part transfer reactions characteristics molecules. A survey main properties intermolecular intramolecular hydrogen both neutral protonated species is proposed. Consequences thermochemistry, particularly discussed. Finally, chemical which may potentially occur inside clusters measurement molecule Examples bond dissociations with hydride alkyl migrations, transport catalysis, tautomerization, cyclization, ring opening nucleophilic substitution illustrate complex chemistry that accompany © 2007 Wiley Periodicals, Inc., Mass Spec Rev 26:775–835,