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A persistent germylyne radical enabling reversible σ-dimerization and diverse bond activation.
Xingyu Yang1,2, Meirong Song2, Liancheng He1,2
1State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, China.
Nature Communications
|May 28, 2026
Summary
Researchers synthesized a stable germylyne radical capable of reversible dimerization, forming a germanium-germanium single bond. This discovery opens new avenues for dynamic covalent bonding and main-group chemistry applications.
Area of Science:
- Main-group chemistry
- Radical chemistry
- Organometallic chemistry
Background:
- Reversible radical dimerization is crucial for bond formation and cleavage.
- Isolating stable heavy carbyne analogues capable of dimerization remains a significant challenge in chemistry.
Purpose of the Study:
- To synthesize and characterize a stable, isolable heavy carbyne analogue.
- To investigate its reversible dimerization process and explore its potential as a synthon for bond activation.
Main Methods:
- Synthesis and characterization of the germylyne radical.
- Variable-temperature Nuclear Magnetic Resonance (NMR) and Electron Paramagnetic Resonance (EPR) spectroscopy.
- X-ray crystallography to elucidate the dimerization pathway.
Main Results:
- An isolable germylyne radical with ambient stability was successfully synthesized.
- The radical undergoes clean, reversible σ-dimerization, forming a Ge-Ge single bond with a moderate bond dissociation enthalpy.
- The dimerization process exhibits a distinct thermochromic response.
- The germylyne radical effectively activates main-group bonds, including chalcogen-chalcogen, phosphorus-phosphorus, and aromatic carbon-chlorine bonds.
Conclusions:
- This study provides direct structural evidence for the dimerization pathway of a heavy carbyne.
- The synthesized germylyne radical serves as a versatile synthon for main-group bond activation.
- This work establishes a novel platform for dynamic covalent bonding in main-group chemistry, with potential applications in stimuli-responsive materials.
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