The hydrostannylation of white phosphorus (P4) allows this crucial industrial precursor to be easily transformed into useful P1 products via direct, ‘one pot’ (or even catalytic) procedures. However, a thorough mechanistic understanding of this transformation has remained elusive, hindering attempts to use this rare example of successful, direct P4 functionalization as a model for further reaction development. Here, we provide a deep and generalizable mechanistic picture for P4 hydrostannylation by combining DFT calculations with in situ31P NMR reaction monitoring and kinetic trapping of previously unobservable reaction intermediates using bulky tin hydrides. The results offer important insights into both how this reaction proceeds and why it is successful and provide implicit guidelines for future research in the field of P4 activation.

中文翻译：

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解开白磷的谜团：实验和计算研究揭示了 P4 氢甲锡烷基化的机制


白磷 (P4) 的氢化锡烷基化使得这种重要的工业前体可以通过直接的“一锅”（甚至催化）程序轻松转化为有用的 P1 产品。然而，对这种转变的彻底机理理解仍然难以捉摸，这阻碍了利用这一罕见的成功直接 P4 功能化例子作为进一步反应开发模型的尝试。在这里，我们通过将 DFT 计算与原位 31 P NMR 反应监测以及使用大体积锡氢化物对以前无法观察到的反应中间体的动力学捕获相结合，提供了 P4 氢甲锡烷基化的深入且可概括的机理图。这些结果为了解该反应如何进行以及为何成功提供了重要见解，并为 P4 激活领域的未来研究提供了隐含的指导。