E. Anklam, H. Mohan, K. Asmus
Dec 16, 1987
Citations
0
Influential Citations
7
Citations
Journal
Helvetica Chimica Acta
Abstract
1-Iodo-2-(methylthio)ethane was synthesized via a ring-opening reaction of thiirane with MeI in MeCN. The S-centered radical cation of this compound undergoes an intermolecular stabilization with the I substituent of a second unattacked substrate molecule to yield an bonded radical cation. The oxidation was initiated by solvent radical cations in irradiated 1,2-dicloroethane and hexane solutions. The 2ρ/ρ* three-electron-bonded species exhibits an optical absorption band at 410 nm, detectable by pulse radiolysis. During its decay, a new, longer-lived absorption band is formed at 380 nm which is assigned to . The latter is suggested to result from anchimeric assistance in the generation of a cyclic sulfonium salt. The radical cations of 1-bromo-and 1-chloro-2-(methylthio)ethane are assumed to undergo raped cyclization to the sulfonium salt without stabilization in any intermolecular S-Br or S-Cl interaction.