Empirical energy - Density relationships for the analysis of substituent effects in chemical reactivity
Author
dc.contributor.author
Pérez, Patricia
Author
dc.contributor.author
Simón-Manso, Y.
Author
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Aizman, Arie
Author
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Fuentealba Rosas, Patricio
Author
dc.contributor.author
Contreras Ramos, Renato
Admission date
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2018-12-20T15:20:36Z
Available date
dc.date.available
2018-12-20T15:20:36Z
Publication date
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2000
Cita de ítem
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Journal of the American Chemical Society, Volumen 122, Issue 19, 2018, Pages 4756-4762
Identifier
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00027863
Identifier
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10.1021/ja994108u
Identifier
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https://repositorio.uchile.cl/handle/2250/158833
Abstract
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Electronic substituent effects may be rationalized in terms of Hammett- like linear relationships between global energy-dependent quantities and local electronic descriptors of reactivity. These linear relationships are framed on a local hard and soft acids and bases (HSAB) principle in accord with previous results reported by Li and Evans [J. Am. Chem. Soc. 1995, 117, 7756]. Chemical substitution is indirectly assessed as local responses at the active center of the substrate, with the Fukui function and local softness as the key quantities within the present approach. This model of chemical substitution has a potential advantage with respect to models based on group properties using the electronegativity equalization principle (EEP), since the transferability of group properties is not required. The formalism is illustrated for the gas-phase basicity of alkylamines, and the gas-phase acidity of alkyl alcohols and alkyl thioalcohols. Our results based on the local HSAB rule agree well