87721-34-4Relevant articles and documents
Synthesis, electrochemistry, and gas-phase photoelectron spectroscopic and theoretical studies of 3,6-bis(perfluoroalkyl)-1,2-dithiins
Lorance, Edward D.,Glass, Richard S.,Block, Eric,Li, Xiaojie
, p. 8110 - 8114 (2003)
3,6-Bis(trifluoromethyl)- and 3,6-bis(pentafluoroethyl)-1,2-dithiin (la,b), the first known perfluoroalkyl-substituted 1,2-dithiins, were synthesized from (Z,Z)-1,4-bis(tert-butylthio)-1,3-butadiene (2) to evaluate the effects of electron-withdrawing groups on the ionization and oxidation potentials of 1,2-dithiins. Analysis of the photoelectron spectra of la and lb provided a basis for assigning orbital compositions. Ab initio calculations on these compounds showed that they adopt a twist geometry as does 1,2-dithiin (1c) itself. Cyclic voltammetric studies on la and lb revealed a reversible oxidation followed by an irreversible oxidation at much more positive potentials than for 1,2-dithiin and 3,6-dimethyl-1,2-dithiin (1d). The oxidation potentials determined electrochemically do not correlate with the ionization potentials determined by photoelectron spectroscopy. This result supports the previously advanced hypothesis that there is a geometry change on electrochemical oxidation leading to a planar radical cation.
Thiirene formation in the reactions of sulfur atoms with alkynes
Verkoczy, Bela,Sherwood, Alden G.,Safarik, Imre,Strausz, Otto P.
, p. 2268 - 2281 (2007/10/02)
The gas phase reactions of S(1D2) and S(3PJ) atoms with alkynes have been studied by photolyzing COS in the presence of CHCH, CF3CCH, and CF3CCCF3.In the reactions with CHCH, CS2, benzene, and thiophene were formed; with CF3CCH, eight products found with disubstituted thiophenes and trisubstituted benzenes as the major products.In the case of CF3CCCF3, only perfluorotetramethylthiophene was detected at low conversion but at long photolysis several new products were observed.Many of the reaction products characterized here have not been reported before.The formation and distribution of the reaction products could be rationalized by an overall mechanism in which the formation of the highly reactive primary adducts, thiirene and thioformylmethylene, is followed by bimolecular reactions yielding the principal end products.The formation of minor products could be explained by secondary photoisomerizations, secondary photolysis, and by secondary decompositions and the secondary reactions of sulfur atoms with primary products.
