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

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

doi:10.1021/jacs.3c11893

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

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

Authors

Kaiyip Chan¹, Fei Ying², Dongyu He¹, Li Yang³, Yanxia Zhao¹, Jing Xie², Ji-Hu Su⁴, Biao Wu³, Xiao-Juan Yang^{1

3}

Affiliations

¹ 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.
² Key Laboratory of Cluster Science of Ministry of Education, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488, China.
³ Key Laboratory of Medicinal Molecule Science and Pharmaceutics Engineering, Ministry of Industry and Information Technology, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488, China.
⁴ CAS Key Laboratory of Microscale Magnetic Resonance and School of Physical Sciences, University of Science and Technology of China, Hefei 230026, China.

PMID: 38241610
DOI: 10.1021/jacs.3c11893

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)₆][LSn:···Sn:L] (1), 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 = N,N-dpp-o-phenylene diamide) with KC₈. The one-electron Sn-Sn bond in 1 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.