Laboratory for Computational Molecular Design, Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland.
J Org Chem. 2012 Mar 2;77(5):2548-52. doi: 10.1021/jo202606v. Epub 2012 Feb 13.
A direct relationship exists between the properties of substituted semibullvalenes and their Cope rearrangement activation barrier. This unique correlation not only enables the determination of kinetic data from ground state information, but also provides a rationalization for the extent to which ground state properties are altered with respect to their "normal" values (i.e., that of their localized Lewis structure). Examination of electron density distribution, geometrical parameters, and J-coupling constant differences between canonical and Lewis structures deliver quantitative evidence for the structure-correlation principle.
取代半环辛二烯的性质与其 Cope 重排活化能垒之间存在直接关系。这种独特的相关性不仅使我们能够从基态信息确定动力学数据，而且还解释了基态性质与其“正常”值（即其局域路易斯结构的值）相比发生变化的程度。对电子密度分布、几何参数和经典结构与路易斯结构之间的 J 耦合常数差异的研究为结构相关原理提供了定量证据。
