TY - JOUR
T1 - Electrochemical and chemical oxidation of dithia-, diselena-, ditellura-, selenathia-, and tellurathiamesocycles and stability of the oxidized species
AU - Evans, Dennis H.
AU - Gruhn, Nadine E.
AU - Jin, Jin
AU - Li, Bo
AU - Lorance, Edward
AU - Okumura, Noriko
AU - Macías-Ruvalcaba, Norma A.
AU - Zakai, Uzma I.
AU - Zhang, Shao Zhong
AU - Block, Eric
AU - Glass, Richard S.
PY - 2010/3/19
Y1 - 2010/3/19
N2 - "Chemical Equation Presented" 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-dithiocane 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+.
AB - "Chemical Equation Presented" 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-dithiocane 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+.
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U2 - 10.1021/jo9026484
DO - 10.1021/jo9026484
M3 - Article
C2 - 20180528
AN - SCOPUS:77949854905
VL - 75
SP - 1997
EP - 2009
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 6
ER -