title: Odd-electron-bonded sulfur radical cations: X-ray structural evidence of a sulfur-sulfur three-electron σ-bond.
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.affiliation: State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, and ‡Centre of Modern Analysis, Nanjing University , Nanjing 210093, China.
authors.forename: Senwang
authors.initials: S
authors.lastname: Zhang
authors.forename: Xingyong
authors.initials: X
authors.lastname: Wang
authors.forename: Yunxia
authors.initials: Y
authors.lastname: Sui
authors.forename: Xinping
authors.initials: X
authors.lastname: Wang
mesh_terms: D018360:Crystallography, X-Ray; D019281:Dimerization; D004583:Electrons; D005609:Free Radicals / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D013455:Sulfur / Q000737:chemistry*
chemical_list: D005609:Free Radicals; D013455:Sulfur