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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.
Angewandte Chemie (International Ed. in English)
|December 16, 2025
Summary
Researchers synthesized novel germyliumylidene complexes, overcoming stabilization challenges. These complexes enable the creation of unique heterobimetallic compounds with potential applications in catalysis.
Area of Science:
- Organometallic Chemistry
- Main Group Chemistry
- Cluster Chemistry
Background:
- Heterobimetallic complexes with heavier tetrylenes are rare due to stabilization issues.
- The inert pair effect limits the stability of heavier tetrylenes and tetryliumylidenes.
Purpose of the Study:
- To synthesize and characterize novel germyliumylidene-containing molecules.
- To explore the reactivity of these molecules in forming heterobimetallic complexes.
- To investigate the stabilization mechanisms in these novel compounds.
Main Methods:
- Incorporation of a chlorogermyliumylidene into a B6 cluster-based diphosphine ligand.
- Reactions with nucleophilic KFeCp(CO)2 and electrophilic AuCl·SMe2.
- Molecular self-assembly and precursor formation for heterobimetallic synthesis.
- X-ray diffraction analysis and computational studies.
Main Results:
- A germyliumylidene-containing unit with a monoanionic charge was successfully synthesized.
- Ambiphilic reactivity was observed, leading to iron-substituted germyliumylidene and an inorganic macrocycle.
- The macrocycle served as a precursor for heterobimetallic complexes with Au─M (M═Mn, Co, W) bonds.
- Ge atom s-donation was identified as the key stabilization factor.
Conclusions:
- Germyliumylidenes can act as effective ancillary ligands in stabilizing heterobimetallic fragments.
- Novel synthetic routes to germyliumylidene-containing compounds and heterobimetallic complexes were established.
- The findings advance the understanding of bonding and stabilization in heavier main group element chemistry.
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