The conceptual replacement of nitrogen with phosphorus in common organic functional groups unlocks new properties and reactivity. The phosphorus‐containing analogues of triazenes are underexplored but offer great potential as flexible and small bite‐angle ligands. This manuscript explores the synthesis and characterisation of a family of air‐stable azophosphine‐borane complexes, and their subsequent deprotection to the free azophosphines. These compounds are structurally characterised, both experimentally and computationally, and highlight the availability of the phosphorus lone pair for coordination. This is confirmed by demonstrating that neutral azophosphines can act as ligands in Ru complexes, and can coordinate as monodentate or bidentate ligands in a controlled manner, in contrast to their nitrogen analogues.

中文翻译：

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偶氮膦：合成、结构和配位化学

在常见有机官能团中用磷概念性地取代氮释放了新的特性和反应性。三氮烯的含磷类似物尚未得到充分研究，但作为灵活的小咬角配体具有巨大的潜力。该手稿探讨了一系列空气稳定的偶氮膦-硼烷配合物的合成和表征，以及它们随后脱保护为游离偶氮膦。这些化合物通过实验和计算进行了结构表征，并强调了磷孤对电子配位的可用性。通过证明中性偶氮膦可以充当Ru配合物中的配体，并且可以以受控方式配位为单齿或二齿配体，与它们的氮类似物相比，证实了这一点。