Wang Yuwen, Szilvási Tibor, Yao Shenglai, Driess Matthias
Metalorganics and Inorganic Materials, Department of Chemistry, Technische Universität Berlin, Berlin, Germany.
Department of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, WI, USA.
Nat Chem. 2020 Sep;12(9):801-807. doi: 10.1038/s41557-020-0518-0. Epub 2020 Aug 17.
In contrast to the well-established transition-metal-mediated activation of white phosphorus (P), the metal-free direct functionalization of P has remained rare. The conversion of P into a reactive zero-valent diphosphorus compound (P) has proven challenging to carry out without relying on metal reactivity. Herein, we describe the facile degradation of P mediated by two divalent silicon atoms in a bis(silylene) scaffold, resulting in a silylene-stabilized zero-valent P complex. The presence of two lone pairs of electrons on each P atom in the silylene-stabilized P complex enables a rich reactivity towards small molecules; reaction of the P species with CO, water or a borane leads to the formation of P-C, P-H or P-B bonds, respectively. Notably, the P complex also serves as a single phosphorus anion (P) transfer reagent towards metal carbonyls and a chlorogermylene compound, leading to the synthetically valuable phosphaketenide (PCO) ligand and a phosphinidene germylene complex, respectively.
与已成熟的过渡金属介导的白磷（P）活化相比，磷的无金属直接官能团化仍然很少见。在不依赖金属反应性的情况下，将磷转化为具有反应活性的零价双磷化合物（P）已被证明具有挑战性。在此，我们描述了在双（硅烯）支架中由两个二价硅原子介导的磷的 facile 降解，从而产生了硅烯稳定的零价磷配合物。硅烯稳定的磷配合物中每个磷原子上存在的两对孤对电子使其对小分子具有丰富的反应活性；该磷物种与一氧化碳、水或硼烷反应分别导致形成P-C、P-H或P-B键。值得注意的是，该磷配合物还作为一种单磷阴离子（P）转移试剂作用于金属羰基化合物和一种氯锗烯化合物，分别生成具有合成价值的磷杂乙炔（PCO）配体和一种磷亚基锗烯配合物。
“facile”常见释义为“容易的；灵巧的” ，这里结合语境暂译为“ facile” ，可根据实际准确含义调整。
