Protic Acidity of Some Aliphatic and Alicyclic Hydrocarbons in the Gas Phase and in Solution. An Empirical and Computational Link

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Title:Protic Acidity of Some Aliphatic and Alicyclic Hydrocarbons in the Gas Phase and in Solution. An Empirical and Computational Link
Creators:
Quintanilla, Esther
Dávalos, Juan Z.
Herrero, Rebeca
Jiménez, Pilar
Alkorta, Ibon
Abboud, José-Luis M.
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 69, 12, pp. 2134-2146
Uncontrolled Keywords:<i>Ab initio</i> calculations, Carbanions, Protic acidity, Alicyclic hydrocarbons, Charge-delocalized anions, Gas-phase reactivity, Thermodynamics, CCSD(T)

Abstract

Here we report the results of the study of a set of thirteen hydrocarbons R-H not leading to extensively charge-delocalized anions R<sup>-</sup> upon ionization, R-H → R<sup>-</sup> + H<sup>+</sup>. It essentially involves the following: (i) The computation at the G2 level of the changes in thermodynamic state functions for this process in the gas phase. The reliability of the computational method was further assessed by comparison with CCSD(T)/Aug-cc-pVTZ results. (ii) A direct comparison of the experimentally available thermodynamic (gas phase) and kinetic (solution) data pertaining to this reaction. (iii) A careful re-examination of the experimental data sets and the Brønsted-type relationships derived therefrom by using the computed thermodynamic data. This treatment suggests the existence of mechanistic features affecting the experimental data and indicates the need for further experimental and computational work. <p>

Title:Protic Acidity of Some Aliphatic and Alicyclic Hydrocarbons in the Gas Phase and in Solution. An Empirical and Computational Link
Creators:
Quintanilla, Esther
Dávalos, Juan Z.
Herrero, Rebeca
Jiménez, Pilar
Alkorta, Ibon
Abboud, José-Luis M.
Uncontrolled Keywords:<i>Ab initio</i> calculations, Carbanions, Protic acidity, Alicyclic hydrocarbons, Charge-delocalized anions, Gas-phase reactivity, Thermodynamics, CCSD(T)
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:69
Number:12
Page Range:pp. 2134-2146
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc20042134UNSPECIFIED
ID Code:2326
Item Type:Article
Deposited On:06 Feb 2009 17:17
Last Modified:06 Feb 2009 16:17

Citation

Quintanilla, Esther; Dávalos, Juan Z.; Herrero, Rebeca; Jiménez, Pilar; Alkorta, Ibon; Abboud, José-Luis M. (2004) Protic Acidity of Some Aliphatic and Alicyclic Hydrocarbons in the Gas Phase and in Solution. An Empirical and Computational Link. Collection of Czechoslovak Chemical Communications, 69 (12). pp. 2134-2146. ISSN 0010-0765

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