Odd-Electron-Bonded Sulfur Radical Cations: X-ray Structural Evidence of a Sulfur-Sulfur Three-Electron σ-Bond

被引：51

作者：

Zhang, Senwang ^{[1
]}

Wang, Xingyong ^{[1
]}

Sui, Yunxia ^{[2
]}

Wang, Xinping ^{[1
]}

机构：

[1] Nanjing Univ, Sch Chem & Chem Engn, State Key Lab Coordinat Chem, Nanjing 210093, Jiangsu, Peoples R China

[2] Nanjing Univ, Ctr Modern Anal, Nanjing 210093, Jiangsu, Peoples R China

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 42期

基金：

中国国家自然科学基金;

关键词：

INTRAMOLECULAR PROTON-TRANSFER; CRYSTAL-STRUCTURES; HYDROXYL RADICALS; SPIN-RESONANCE; ORGANIC SULFIDES; OXIDATION; METHIONINE; OXYGEN; COMPLEXES; MECHANISM;

D O I：

10.1021/ja507918c

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The one-electron oxidations of 1,8-chalcogen naphthalenes Nap(SPh)(2) (1) and Nap(SPh)(SePh) (2) lead to the formation of persistent radical cations 1(center dot+) and 2(center dot+) in solution. EPR spectra, UV-vis absorptions, and DFT calculations show a three-electron sigma-bond in both cations. The former cation remains stable in the solid state, while the latter dimerizes upon crystallization and returns to being radical cations upon dissolution. This work provides conclusive structural evidence of a sulfur-sulfur three-electron sigma-bond (in 1(center dot+)) and a rare example of a persistent heteroatomic three-electron sigma-bond (in 2(center dot+)).

引用

页码：14666 / 14669

页数：4

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