Isolation of Germyliumylidene‐Stabilized Heteronuclear Transition Metal Complexes

Abstract

Abstract Heterobimetallic complexes featuring heavier tetrylenes and tetryliumylidenes are scarce due to their limited stabilization capability stemming from the inert pair effect. Herein, we report that the incorporation of a chlorogermyliumylidene into a dianionic B 6 cluster‐based diphosphine ligand allows access to the germyliumylidene‐containing unit carrying a monoanionic charge. This molecule exhibits ambiphilic reactivity toward nucleophilic KFeCp(CO) 2 and electrophilic AuCl·SMe 2 , rendering the iron‐substituted germyliumylidene and inorganic macrocycle via molecular self‐assembly, respectively. The latter is found to serve as a precursor, by reacting with metalates, for the construction of heterobimetallic complexes featuring Au─M (M═Mn, Co, W) bonds. X‐ray diffraction analysis and computational studies elucidate that those heterobimetallic fragments are stabilized by s‐donation from the Ge atom, demonstrating the capability of the germyliumylidene as an ancillary supporting ligand.