Phosphagermyenylidene: A Heavier Analog of Isonitrile

Abstract Phosphagermyenylidenes (R − P = Ge), as heavier analogs of isonitriles, whether in their free state or as complexes with a Lewis base, have not been previously identified as isolable entities. In this study, we report the synthesis of a stable monomeric phosphagermyenylidene within the coordination sphere of a Lewis base under ambient conditions. This species was synthesized by Lewis base-induced de-dimerization of a cyclic phosphagermyenylidene dimer or via Me3SiCl elimination in a phosphinochlorogermylene framework. The deliberate integration of a bulky, electropositive N-heterocyclic boryl group at the phosphorus site, combined with coordination stabilization by a cyclic (alkyl)(amino)carbene at the low-valent germanium site, effectively mitigated its natural tendency towards oligomerization. Structural analyses and theoretical calculations have demonstrated that this unprecedented species features a P = Ge double bond, characterized by conventional electron-sharing π and σ bonds, complemented by lone pairs at both the phosphorus and germanium atoms. Preliminary reactivity studies show that this base-stabilized phosphagermyenylidene demonstrates facile release of ligands at the Ge atom, coordination to silver through the lone pair on P, and versatile reactivity including both (cyclo)addition and cleavage of the P = Ge double bond.