A further exploration of a nucleophilicity index based on the gas-phase ionization potentials
| Contribuinte(s) |
UNIVERSIDADE DE SÃO PAULO |
|---|---|
| Data(s) |
20/10/2012
20/10/2012
2008
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| Resumo |
An empirical nucleophilicity index based on the gas-phase ionization potentials has been recently shown to be useful categorizing and settling the nucleophilicity power of a series of captodative ethylenes reacting in cycloaddition reactions (L.R. Domingo, E. Chamorro, P. Perez, Journal of Organic Chemistry 73 (2008) 4615-4624). In the present work, the applicability of such model is tested within a broader series of substituted alkenes, substituted aromatic compounds and simple nucleophilic molecules. This index obtained within a Koopman`s theorem framework has been evaluated here in both gas and solution phases for several well-known nucleophiles. These results are found to be linearly correlated. Finally, the feasibility of the predictive character of this index has been discussed in comparison to the available experimental nucleophilicities of some amines in water. These results further support and validate the usefulness of such approximation in the modeling of the global nucleophilicity. (C) 2008 Elsevier B.V. All rights reserved. Fondecyt Projects[1060961] Fondecyt Projects Fondecyt Projects Fondecyt Projects[1070378] Fondecyt Projects[7070051] Fondecyt Projects Ministerio de Educacion y Ciencia of the Spanish Government Ministerio de Educacion y Ciencia of the Spanish Government[CTQ2006-14297/BQU] Universidad Andres Bello (UNAB) Universidad Andres Bello (UNAB)[DI 21-06/R] Universidad Andres Bello (UNAB)[45-08/R] Universidad Andres Bello (UNAB) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) FAPESP |
| Identificador |
JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM, v.865, n.1/Mar, p.68-72, 2008 0166-1280 http://producao.usp.br/handle/BDPI/29595 10.1016/j.theochem.2008.06.022 |
| Idioma(s) |
eng |
| Publicador |
ELSEVIER SCIENCE BV |
| Relação |
Journal of Molecular Structure-theochem |
| Direitos |
restrictedAccess Copyright ELSEVIER SCIENCE BV |
| Palavras-Chave | #nucleophilicity #gas-phase ionization potential #electrophilicity #electron-withdrawing group effects #electron-releasing group effects #DIELS-ALDER REACTIONS #QUANTITATIVE CHARACTERIZATION #CYCLOADDITION REACTIONS #LOCAL ELECTROPHILICITY #CHEMICAL-REACTIVITY #PROTON AFFINITIES #PHILICITY #SCALE #REGIOSELECTIVITY #SELECTIVITY #Chemistry, Physical |
| Tipo |
article original article publishedVersion |
