Krygowski T M, Zachara J E, Ośmiałowski B, Gawinecki R
Department of Chemistry, Warsaw University, Pasteura 1, 02-093 Warsaw, Poland.
J Org Chem. 2006 Sep 29;71(20):7678-82. doi: 10.1021/jo061068l.
The Clar model predicting stability and electron distribution in benzenoid hydrocarbons seems to be also a good predictor for related properties in lithium o-acylphenolates and to a lesser extent in the phenols themselves. This conclusion is based on analysis of geometry changes in the analogues of naphthalene, phenanthrene, anthracene, and triphenylene, where benzene rings are systematically replaced with a quasi-ring formed as a beta-ketoenol or beta-ketoenolate complex with a lithium cation, i.e., where CH-CH-CH fragments are replaced with O...Li...O or O...H...O fragments. These systems were optimized at the MP2/6-31G(2d,p) level of theory. The energy of bond separation reactions in line with aromaticity indices HOMA and NICSs supported the above statement.
用于预测苯型烃稳定性和电子分布的克拉尔模型似乎也是锂邻酰基苯酚盐相关性质的良好预测模型，在一定程度上对苯酚本身的相关性质也适用。这一结论是基于对萘、菲、蒽和三亚苯类似物几何结构变化的分析得出的，其中苯环被与锂阳离子形成的β-酮烯醇或β-酮烯醇盐配合物构成的准环系统取代，即CH-CH-CH片段被O...Li...O或O...H...O片段取代。这些体系在MP2/6-31G(2d,p)理论水平上进行了优化。符合芳香性指数HOMA和NICSs的键分离反应能量支持了上述说法。
