Synthesis, structural characterization, and reactivity of homocatenated Ga₄ complexes with unsaturated Ga-Ga=Ga-Ga chains.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 41429787.
- Also identified by DOI 10.1038/s41467-025-67892-1 and PMC identifier 12749812.
- Licence recorded as CC BY-NC-ND.
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Abstract
The homocatenation of electron-deficient Group 13 metals to form metal-metal multiple bonds through covalent self-assembly remains extremely challenging. Herein we demonstrate the synthesis and characterizations of N-heterocyclic carbene (NHC)-stabilized digallyl digallenes (1a and 1b), which exhibit unsaturated Ga-Ga=Ga-Ga chains with trans-bent geometries. These compounds were synthesized through salt-metathesis reactions using Cp*Ga, (L<sup>1</sup>)K<sub>2</sub>/(L<sup>2</sup>)Li<sub>2</sub>, and 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (IiPr). Employing both experimental and computational techniques, our investigation reveals that the chain elongation of 1a was initiated by the in-situ generation of a gallium(I) carbene analog [(L<sup>1</sup>)GaK]. Additionally, the reactivity of compound 1a with I<sub>2</sub>, PhS-SPh, Ph<sub>3</sub>P = S, and Ph<sub>2</sub>C = O was explored, leading to the formation of tetra-gallium subhalides (4), disulfide addition product (5), a gallium thiirane analog (6), and a [2 + 2] cycloaddition product (7), respectively.