由对苯二胺配体稳定的单电子（2c/1e）锡···锡键

One-Electron (2c/1e) Tin···Tin Bond Stabilized by -Phenylenediamido Ligands.

作者信息

Chan Kaiyip, Ying Fei, He Dongyu, Yang Li, Zhao Yanxia, Xie Jing, Su Ji-Hu, Wu Biao, Yang Xiao-Juan

机构信息

Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an 710069, China.

Key Laboratory of Cluster Science of Ministry of Education, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488, China.

出版信息

J Am Chem Soc. 2024 Jan 31;146(4):2333-2338. doi: 10.1021/jacs.3c11893. Epub 2024 Jan 19.

DOI:10.1021/jacs.3c11893

PMID:38241610

Abstract

Odd-electron bonds, i.e., the two-center, three-electron (2c/3e), or one-electron (2c/1e) bonds, have attracted tremendous interest owing to their novel bonding nature and radical properties. Herein, complex [K(THF)][LSn:···Sn:L] (), featuring the first and unsupported 2c/1e Sn···Sn σ-bond with a long distance (3.2155(9) Å), was synthesized by reduction of stannylene [LSn:] (L = ,-dpp--phenylene diamide) with KC. The one-electron Sn-Sn bond in was confirmed by the crystal structure, DFT calculations, EPR spectroscopy, and reactivity studies. This compound can be viewed as a stabilized radical by delocalizing to two metal centers and can readily mediate radical reactions such as C-C coupling of benzaldehyde.

摘要

奇电子键，即双中心三电子（2c/3e）或单电子（2c/1e）键，因其新颖的键合性质和自由基特性而引起了极大的关注。在此，通过用KC还原亚锡烯[LSn:]（L = ，-dpp--亚苯基二酰胺）合成了配合物[K(THF)][LSn:···Sn:L]（），其具有首个无支撑的长距离（3.2155(9) Å）2c/1e Sn···Sn σ键。通过晶体结构、密度泛函理论计算、电子顺磁共振光谱和反应性研究证实了中的单电子Sn-Sn键。该化合物可通过离域到两个金属中心而被视为一种稳定的自由基，并且能够轻易介导自由基反应，如苯甲醛的C-C偶联反应。