Synthesis and Reactivity of a Crystalline Zinc–cAAC Radical
Abstract
AbstractReaction 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.
Article Details
Authors (5)
Shuilian Xu
Key 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
Yizhen Chen
Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, Guangdong Basic Research Center of Excellence for Functional Molecular Engineering, School of Chemistry, IGCME
Shengjie Jiang
Key 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
Gengwen Tan
Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, Guangdong Basic Research Center of Excellence for Functional Molecular Engineering, School of Chemistry, IGCME
Xin Xu