title: Electrochemical and chemical oxidation of dithia-, diselena-, ditellura-, selenathia-, and tellurathiamesocycles and stability of the oxidized species.
abstract: The diverse electrochemical and chemical oxidations of dichalcogena-mesocycles are analyzed, broadening our understanding of the chemistry of the corresponding radical cations and dications. 1,5-Diselenocane and 1,5-ditellurocane undergo reversible two-electron oxidation with inverted potentials analogous to 1,5-dithiocane. On the other hand, 1,5-selenathiocane and 1,5-tellurathiocane undergo one-electron oxidative dimerization. The X-ray crystal structures of the Se-Se dimer of the 1,5-selenathiocane one-electron oxidized product and the monomeric two-electron oxidized product (dication) of 1,5-tellurathiocane are reported. 1,5-Dithiocanes and 1,5-diselenocanes with group 14 atoms as ring members undergo irreversible oxidation, unlike the reversible two-electron oxidation of the corresponding silicon-containing 1,5-ditellurocanes. These results demonstrate the chemical consequences of the dication stabilities Te(+)-Te(+) > Se(+)-Se(+) > S(+)-S(+), as well as Se(+)-Se(+) > Se(+)-S(+) and Te(+)-Te(+) > Te(+)-S(+).
authors.affiliation: Department of Chemistry, The University of Arizona, Tucson, Arizona 85721, USA. evansd@purdue.edu
authors.forename: Dennis H
authors.initials: DH
authors.lastname: Evans
authors.forename: Nadine E
authors.initials: NE
authors.lastname: Gruhn
authors.forename: Jin
authors.initials: J
authors.lastname: Jin
authors.forename: Bo
authors.initials: B
authors.lastname: Li
authors.forename: Edward
authors.initials: E
authors.lastname: Lorance
authors.forename: Noriko
authors.initials: N
authors.lastname: Okumura
authors.forename: Norma A
authors.initials: NA
authors.lastname: Macías-Ruvalcaba
authors.forename: Uzma I
authors.initials: UI
authors.lastname: Zakai
authors.forename: Shao-Zhong
authors.initials: SZ
authors.lastname: Zhang
authors.forename: Eric
authors.initials: E
authors.lastname: Block
authors.forename: Richard S
authors.initials: RS
authors.lastname: Glass