Origin of Substituent Effects in Edge-to-Face Aryl-Aryl Interactions.
Origin of Substituent Effects in Edge-to-Face Aryl-Aryl Interactions.
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DOI：
10.1080/00268970802537614
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发表时间：
2009-01-01
影响因子：
1.7
通讯作者：
Houk KN
中科院分区：
文献类型：
--
作者：
Wheeler SE;Houk KN
使用现代密度泛函理论研究了苯二聚体边对面构型中的取代效应。已使用具有大基组的从头计算方法计算了未取代二聚体的精确相互作用势能曲线。边对面苯二聚体的推荐结合能为 2.31 kcal mol-1，根据平衡校正 CCSD(T)/aug-cc-pVTZ 理论水平估计。对于边环和面环取代的二聚体，相互作用能与取代基的 σm 相关，表明取代基效应可以用简单的静电效应定性地理解，尽管在后一种情况下色散会导致数据中的一些分散。与苯二聚体中取代基效应的流行模型相反，取代环的π-系统的极化不会引起取代基效应。对于边缘环取代的二聚体，取代基效应源自取代环上的氢与面环的π云之间的差异静电相互作用以及取代基与未取代环的直接相互作用。对于面环取代的二聚体，取代基效应源自取代基与边缘环的直接静电和色散相互作用。 σm > 0.12 的取代基有利于边缘环取代，而 σm < 0.12 则优选在面环上取代。
Substituent effects in the edge-to-face configuration of the benzene dimer have been studied using modern density functional theory. An accurate interaction potential energy curve has been computed for the unsubstituted dimer using ab initio methods with large basis sets. The recommended binding energy for the edge-to-face benzene dimer is 2.31 kcal mol-1, estimated at the counterpoise-corrected CCSD(T)/aug-cc-pVTZ level of theory. For both edge-ring and face-ring-substituted dimers, interaction energies correlate with σm for the substituents, indicating that substituent effects can be understood qualitatively in terms of simple electrostatic effects, although in the latter case dispersion results in some scatter in the data. In contrast to prevailing models of substituent effects in benzene dimers, polarization of the π-system of the substituted ring does not induce substituent effects. For edge-ring-substituted dimers, substituent effects arise from differential electrostatic interactions between the hydrogens on the substituted ring and the π-cloud of the face ring and direct interactions of the substituents with the unsubstituted ring. For face-ring-substituted dimers, substituent effects arise from direct electrostatic and dispersion interactions of the substituents with the edge ring. Substituents with σm > 0.12 favor edge ring substitution while for σm < 0.12 substitution on the face ring is preferred.
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影响因子：
15
作者：
Birman, Vladimir B.;Jiang, Hui;Uffman, Eric W.
通讯作者：
Uffman, Eric W.
影响因子：
16.6
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通讯作者：
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作者：
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通讯作者：
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影响因子：
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作者：
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