Empirical Energy−Density Relationships for the Analysis of Substituent Effects in Chemical Reactivity
Empirical Energy−Density Relationships for the Analysis of Substituent Effects in Chemical Reactivity
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用于分析化学反应中取代基效应的经验能量-密度关系
DOI：
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发表时间：
2000
期刊：
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通讯作者：
R. Contreras
中科院分区：
文献类型：
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作者：
P. Pérez;Y. Simón;A. Aizman;P. Fuentealba;R. Contreras
电子取代效应可以根据全局能量相关量和反应性的局部电子描述符之间的类似哈米特的线性关系来合理化。这些线性关系基于局部硬酸和软酸碱 (HSAB) 原理，与 Li 和 Evans 先前报告的结果一致 [J.是。化学。苏克。 1995, 117, 7756]。化学替代被间接评估为基材活性中心的局部响应，其中福井功能和局部柔软度作为本方法中的关键量。这种化学取代模型相对于基于使用电负性均衡原理 (EEP) 的基团特性的模型具有潜在优势，因为不需要基团特性的可转移性。该形式说明了烷基胺的气相碱性以及烷基醇和烷基硫醇的气相酸性。我们根据当地 HSAB 规则得出的结果与通过...获得的结果非常吻合。
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 with those obtained f...