A formal E-selective hydrophosphination of terminal and internal alkynes catalyzed by a well-defined [Co(PMe₃)₄] (A) complex is achieved under mild conditions in good-to-excellent yield. The reaction does not require any additives and/or external base for an efficient hydrophosphination reaction. The reaction provided excellent scope and good functional tolerance. Detailed spectroscopic analysis (NMR, EPR, and UV–vis) revealed that the low valent cobalt(0) complex undergoes oxidative addition with diphenylphosphine, followed by hydrometalation with alkyne, and subsequent reductive elimination led to the expected product. The detailed spectroscopic analyses along with the isotopic labeled experiments facilitate to intercept the active intermediates that are involved in the catalytic cycle, which are detailed. It was revealed that the suprafacial (vide infra) delivery of H and phosphorus to π-alkynes in a syn-fashion led to formal E-vinyl phosphine.

中文翻译：

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精细定义的钴催化炔烃的电子选择性加氢磷酸化的机理研究

正式Ë通过良好定义的[CO（PME催化末端和内部炔烃-选择性hydrophosphination ₃）₄ ]（甲）复合物可在温和条件下以良好至优异的产量获得。该反应不需要任何添加剂和/或外部碱即可进行有效的磷酸化反应。该反应提供了优异的范围和良好的功能耐受性。详细的光谱分析（NMR，EPR和UV-vis）表明，低价钴（0）配合物与二苯膦进行氧化加成反应，然后与炔烃进行加氢金属化反应，随后进行还原消除反应生成了预期的产物。详细的光谱分析以及同位素标记的实验有助于拦截催化循环中涉及的活性中间体，对此进行了详细介绍。揭示了H和磷在合成气中向π炔的表面（红外）传递。-时尚导致正式的E-乙烯基膦。