In contrast to the well-established transition-metal-mediated activation of white phosphorus (P₄), the metal-free direct functionalization of P₄ has remained rare. The conversion of P₄ into a reactive zero-valent diphosphorus compound (P₂) has proven challenging to carry out without relying on metal reactivity. Herein, we describe the facile degradation of P₄ mediated by two divalent silicon atoms in a bis(silylene) scaffold, resulting in a silylene-stabilized zero-valent P₂ complex. The presence of two lone pairs of electrons on each P atom in the silylene-stabilized P₂ complex enables a rich reactivity towards small molecules; reaction of the P₂ species with CO₂, water or a borane leads to the formation of P–C, P–H or P–B bonds, respectively. Notably, the P₂ 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.

与此相反，以白色的磷（P的行之有效的过渡金属介导的激活₄）中，P的不含金属的直接官能₄一直保持罕见。已经证明，在不依赖金属反应性的情况下，将P ₄转化为反应性的零价二磷化合物（P ₂）具有挑战性。在本文中，我们描述了在双（甲硅烷基）支架中由两个二价硅原子介导的P ₄的容易降解，从而产生了亚甲硅烷基稳定的零价P ₂络合物。在亚甲硅烷基稳定的P ₂络合物中，每个P原子上都存在两个孤对电子，这使得它们对小分子具有很强的反应性。P的反应₂种具有CO ₂，水或硼烷的物质分别导致形成P–C，PH–H或PB–键。值得注意的是，在P ₂复杂也用作单磷阴离子（P ^- ）朝向金属羰基转移试剂和chlorogermylene化合物，导致合成有价值phosphaketenide（PCO ^- ）配位体和分别亚膦锗烯复杂。