Topology-Driven Physicochemical Properties of pi-Electron Systems.1.Does the Clar Rule Work in Cyclic pi-Electron Systems with the Intramolecular Hydrogen or Lithium Bond?

摘要

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.