Transition‐metal‐mediated hydride transfer reactions are fundamental steps in olefin polymerization and isomerization processes. β‐Hydride elimination/migratory insertion sequence and ligand‐to‐ligand hydrogen transfer mechanism have been proposed for these reactions. We have performed comprehensive theoretical studies on prototype 1,4‐hydride transfer reactions mediated by the Cp*M(III) complexes (M = Co, Rh, Ir). Depending on the metal center, the reaction courses are quite divergent, ranging from dynamically concerted to explicitly stepwise manner. A More O'Farrell–Jencks‐type plot is suggested to demonstrate the perturbation to the mechanistic continuum from the significant dynamic effects.

中文翻译：

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Cp * M（III）配合物（M = Co，Rh，Ir）介导的分子内氢化物转移反应的不同途径和动力学效应†

过渡金属介导的氢化物转移反应是烯烃聚合和异构化过程的基本步骤。已经为这些反应提出了β-氢化物消除/迁移插入序列和配体-配体氢转移机制。我们已经对由Cp * M（III）配合物（M = Co，Rh，Ir）介导的原型1,4-氢化物转移反应进行了全面的理论研究。根据金属中心的不同，反应过程会有所不同，从动态协调到明确的逐步方式不等。建议使用更多的O'Farrell-Jencks型图来说明显着动力效应对机械连续体的扰动。