This research presents an adaptive catalyst engineered to optimize hydrogen activation and transfer, demonstrated through its application in the semihydrogenation of alkynes. The catalyst is distinguished by a unique ligand pocket that precisely manipulates H₂ dynamics and substrate interactions. Its ability to adjust to solvent variations ensures the selective synthesis of cis- and trans-alkenes directly from alkynes without reliance on selectivity-altering additives. Our extensive mechanistic study sheds light on the critical influence of the solvent in guiding hydrogen transfer mechanisms, revealing an unconventional outer sphere hydrogenation process. The reversible nature of the catalyst and its robust performance over repeated cycles represent a significant advancement in controlled hydrogen catalysis. This progress highlights the feasibility of selectively producing both kinetic and thermodynamic products, setting a new standard for efficiency and versatility in catalytic processes.

中文翻译：

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控制炔烃自适应半氢化中的氢转移动力学：揭示和指导外球与内球机制


这项研究提出了一种旨在优化氢活化和转移的自适应催化剂，并通过其在炔烃半加氢中的应用得到证明。该催化剂的特点是具有独特的配体袋，可精确控制 H2 动力学和底物相互作用。其适应溶剂变化的能力确保直接从炔烃选择性合成顺式和反式烯烃，而不依赖于改变选择性的添加剂。我们广泛的机理研究揭示了溶剂在引导氢转移机制中的关键影响，揭示了非常规的外层氢化过程。该催化剂的可逆性质及其在重复循环中的稳健性能代表了受控氢催化领域的重大进步。这一进展凸显了选择性生产动力学和热力学产品的可行性，为催化过程的效率和多功能性设定了新标准。