Synthesis and Reactivity of a Crystalline Zinc–cAAC Radical
Reaction of L<sup>Am</sup>ZnI [L<sup>Am</sup> = <sup>t</sup>BuC(N-DIPP)<sub>2</sub>, DIPP = 2,6-<sup>i</sup>Pr<sub>2</sub>-C<sub>6</sub>H<sub>3</sub>] with KC<sub>8</sub> in the presence of cyclic (alkyl)(amino)carbene (cAAC) affords a stable radical complex [L<sup>Am</sup>Zn(cAAC)]<sup>•</sup> (3). Single-crystal structural analysis of 3 shows a short Zn─C bond and concomitant elongation of C─N bond within the cAAC ligand, indicating a significant π-backbonding from the metal to the cAAC ligand. EPR spectroscopy and DFT calculations reveal that the spin density is mainly localized on the carbenic carbon atom, with a small portion on the zinc center. Complex 3 exhibits zinc-centered radical reactivity as demonstrated by reactions with 2,2,6,6-tetramethyl-1-piperidinyloxy, iodobenzene, trimethylsilyl azide, and [FeCp(CO)<sub>2</sub>]<sub>2</sub>, all of which occur at the zinc center and yield the corresponding Zn(II) complexes.
Authors
- Gengwen Tan (ORCID: https://orcid.org/0000-0002-6972-2197)
- Yizhen Chen (ORCID: https://orcid.org/0000-0002-8499-2013)
- Shengjie Jiang (ORCID: https://orcid.org/0000-0003-2552-8736)
- Xin Fang Xu (ORCID: https://orcid.org/0000-0003-2426-9816)
- Shuilian Xu
Institutions
- Sun Yat-sen University (CN)
- Soochow University (CN)
Publication Details
- Journal
- Angewandte Chemie International Edition
- Published
- 2025-09-10
- DOI
- https://doi.org/10.1002/anie.202515723
- Citations
- 1
- Primary Topic
- Organometallic Complex Synthesis and Catalysis
- Type
- article
- Field-Weighted Citation Impact
- 0.94