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Odd-electron-bonded sulfur radical cations: X-ray structural evidence of a sulfur-sulfur three-electron σ-bond

Journal Article


Abstract


  • 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•+).

Authors


  •   Zhang, Senwang (external author)
  •   Wang, Xingyong
  •   Sui, Yunxia (external author)
  •   Wang, Xinping (external author)

Publication Date


  • 2014

Geographic Focus


Citation


  • Zhang, S., Wang, X., Sui, Y. & Wang, X. (2014). Odd-electron-bonded sulfur radical cations: X-ray structural evidence of a sulfur-sulfur three-electron σ-bond. Journal of the American Chemical Society, 136 (42), 14666-14669.

Scopus Eid


  • 2-s2.0-84908391607

Ro Metadata Url


  • http://ro.uow.edu.au/smhpapers/3912

Has Global Citation Frequency


Number Of Pages


  • 3

Start Page


  • 14666

End Page


  • 14669

Volume


  • 136

Issue


  • 42

Place Of Publication


  • United States

Abstract


  • 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•+).

Authors


  •   Zhang, Senwang (external author)
  •   Wang, Xingyong
  •   Sui, Yunxia (external author)
  •   Wang, Xinping (external author)

Publication Date


  • 2014

Geographic Focus


Citation


  • Zhang, S., Wang, X., Sui, Y. & Wang, X. (2014). Odd-electron-bonded sulfur radical cations: X-ray structural evidence of a sulfur-sulfur three-electron σ-bond. Journal of the American Chemical Society, 136 (42), 14666-14669.

Scopus Eid


  • 2-s2.0-84908391607

Ro Metadata Url


  • http://ro.uow.edu.au/smhpapers/3912

Has Global Citation Frequency


Number Of Pages


  • 3

Start Page


  • 14666

End Page


  • 14669

Volume


  • 136

Issue


  • 42

Place Of Publication


  • United States