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Published on: April 19, 2019
Isolation of Germyliumylidene-Stabilized Heteronuclear Transition Metal Complexes
Penglong Wang1, Nigam Sriyansh1, Rei Kinjo1
1School of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological University, Singapore, 637371, Singapore.
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 B6 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·SMe2, 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.
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