CHEMISTRY OF GAS PHASE

Author: QUINTANILLA LUJÁN ESTHER.
Year: 2004.
University: AUTÓNOMA DE MADRID [www.uam.es].
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD CIENCIAS.

Summary: This thesis presents the results of studies conducted in the laboratory Resonance Ciclotrónica of ions (FT ICR) of the Institute of Physical Chemistry Rocasolano CSIC. The design of all studies is essentially experimental, as befits a laboratory of this kind. All of this was financed through the projects BQU2000-1497 and BQU2003 -5827 of the DGICYT. In most of the work was applied FT ICR technique to the study of transfer processes protónica in gaseous phase. Given the absence of solvent can be considered to reflect properties "intrinsic" of the species involved. One common denominator of all of them has been the search for relationships between structure and thermodynamic stability of neutral and ionic species, including the influence of isotopic effects. So more precise, the papers presented are: 1. The experiment of a secondary isotope effect on a balance transfer protónica using pyridine and pyridine deuterada. Regardless of its intrinsic interest, the determination of an effect of this kind is both a challenge and an experimental test of the quality of the instrumentation. 2. The protonación and desprotonación of cubilamina, a derivative of Cuban gas phase and in solution. As detailed later, this species introduced structural features impressive conferring unusual interest to what would otherwise be a series of experiments "almost routine." 3. The acidity of some cyclical and alicyclic saturated hydrocarbons in gas phase and in solution. Formally it is a purely computational work (calculated at G2 and CCSD (T)). In fact, the spirit is "experimental", in so far as they were used thermodynamic functions of state obtained by theoretical methods for, among other things, clarify issues raised by some property characteristics, well established experimentally, the carbaniones aliphatic. 4. The discovery that pivaladehido, trimetilacetaldehido was isomeriza in gas phase, in terms of acid catalysis to metilisopropilcetona. This process begins with the monoprotonación of aldehyde, unlike what seems to occur in solution, which puts at stake the reaction intermediate diprotonados. The theoretical mechanistic studies carried out in the UAM, to justify and rationalize the experimental results.