Utility of the Nudged Elastic Band Method in Identifying the Minimum Energy Path of an Elementary Organometallic Reaction Step

The nudged elastic band (NEB) method has been used to re-examine the oxidative addition step in the classic rhodium-catalyzed hydroacylation reaction. Numerous additional intermediates were found on a pathway that is lower in energy than that originally reported. This study illustrates the potential limitations of the traditional approach to locating transition states in which a chemical-intuition-guided linear or quadratic synchronous transit is used to estimate the high point of the reaction trajectory. Utilization of that approach constrains the search so that the actual transition state and other possible intermediates and transition states may be missed.

本研究采用 nudged弹性带法（nudged elastic band，NEB），重新审视了经典铑催化加氢酰化反应中的氧化加成步骤。研究在一条能量低于原文献报道路径的反应途径上，发现了诸多额外中间体。该研究揭示了传统过渡态搜寻方法的潜在局限性：这类方法通过基于化学直觉引导的线性或二次同步位移法估算反应轨迹的最高点。此类方法会对搜索过程施加约束，进而可能导致实际过渡态及其他潜在中间体与过渡态被遗漏。