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Odd-electron-bonded sulfur radical cations: X-ray structural evidence of a sulfur-sulfur three-electron σ-bond.
Zhang, Senwang; Wang, Xingyong; Sui, Yunxia; Wang, Xinping.
Afiliação
  • Zhang S; State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, and ‡Centre of Modern Analysis, Nanjing University , Nanjing 210093, China.
J Am Chem Soc ; 136(42): 14666-9, 2014 Oct 22.
Article em En | MEDLINE | ID: mdl-25299728
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(•+) and 2(•+) in solution. EPR spectra, UV-vis absorptions, and DFT calculations show a three-electron σ-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 σ-bond (in 1(•+)) and a rare example of a persistent heteroatomic three-electron σ-bond (in 2(•+)).
Assuntos

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Assunto principal: Enxofre / Elétrons Idioma: En Ano de publicação: 2014 Tipo de documento: Article

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Assunto principal: Enxofre / Elétrons Idioma: En Ano de publicação: 2014 Tipo de documento: Article