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Synthesis and Reactivity of a Crystalline Zinc-cAAC Radical
Shuilian Xu1, Yizhen Chen2, Shengjie Jiang1
1Key Laboratory of Organic Synthesis of Jiangsu Province & State Key Laboratory of Bioinspired Interfacial Materials Science, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, P.R. China.
None:
Reaction of LAmZnI [LAm = tBuC(N-DIPP)2, DIPP = 2,6-iPr2-C6H3] with KC8 in the presence of cyclic (alkyl)(amino)carbene (cAAC) affords a stable radical complex [LAmZn(cAAC)]• (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)2]2, all of which occur at the zinc center and yield the corresponding Zn(II) complexes.
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