Electrochemical and chemical oxidation of dithia-, diselena-, ditellura-, selenathia-, and tellurathiamesocycles and stability of the oxidized species.
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(+).
Evans
Dennis H
DH
Department of Chemistry, The University of Arizona, Tucson, Arizona 85721, USA. evansd@purdue.edu
Gruhn
Nadine E
NE
Jin
Jin
J
Li
Bo
B
Lorance
Edward
E
Okumura
Noriko
N
Macías-Ruvalcaba
Norma A
NA
Zakai
Uzma I
UI
Zhang
Shao-Zhong
SZ
Block
Eric
E
Glass
Richard S
RS