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Formation and Characterization of 1-Substituted 1,2-Dithiolanyl Radicals By Laser Flash Photolysis

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Photolyses of 1-alkylthio-9-propanethiols, 1,9-propanedithiol and 1-phenylthio-9-propanethiol in acetonitrile, 2-propanol or aqueous mixtures of these solvents lead to five membered cyclic sulfuranyl radicals of the type [R-S- S- CH2 - CH2 - CH2| which exhibit characteristic uv/vis absorption spectra. These 1-substituted 1,2-dithiolanyl radicals are formed by intramolecular cyclization of the primarily formed thiyl radicals generated by S-H- bond cleavage in the excited starting material. The wavelength of the absorption maximum observed for these transients depends on the nature of the substituent R on the sulfur atom (R=H, alkyl, aryl).

Affiliations: 1: Hahn-Meitner Institut Berlin GmbH Bereich Strahlenchemie Glienicker Strasse 100, D-1000 Berlin 39, FRG


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