Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands.
Institute of Molecules and Materials (IMM), Radboud University, Heyendaalseweg 135, 6525 AJ, Nijmegen, The Netherlands.
Angew Chem Int Ed Engl. 2017 Aug 14;56(34):10070-10086. doi: 10.1002/anie.201701486. Epub 2017 Jul 17.
The activation strain or distortion/interaction model is a tool to analyze activation barriers that determine reaction rates. For bimolecular reactions, the activation energies are the sum of the energies to distort the reactants into geometries they have in transition states plus the interaction energies between the two distorted molecules. The energy required to distort the molecules is called the activation strain or distortion energy. This energy is the principal contributor to the activation barrier. The transition state occurs when this activation strain is overcome by the stabilizing interaction energy. Following the changes in these energies along the reaction coordinate gives insights into the factors controlling reactivity. This model has been applied to reactions of all types in both organic and inorganic chemistry, including substitutions and eliminations, cycloadditions, and several types of organometallic reactions.
激活应变或变形/相互作用模型是分析决定反应速率的激活势垒的工具。对于双分子反应,激活能是将反应物扭曲成过渡态中它们具有的几何形状所需的能量与两个扭曲分子之间的相互作用能之和。将分子扭曲所需的能量称为激活应变或变形能。该能量是激活势垒的主要贡献者。当这种激活应变被稳定的相互作用能克服时,过渡态就会发生。沿着反应坐标跟踪这些能量的变化可以深入了解控制反应性的因素。该模型已应用于有机和无机化学中的各种类型的反应,包括取代和消除、环加成和几种类型的有机金属反应。