Electron paramagnetic resonance (EPR) study of γ-radiation-induced radicals in 1,3,5-trithiane and its derivatives

Radicals formed in γ-irradiated 1,3,5-trithiane (TT) and its three derivatives, α- and β-2,4,6-trimethyl-1,3,5-trithiane (α-TMT and β-TMT), and 2,4,6-trimethyl-2,4,6-triphenyl-1,3,5-trithiane (TMTPT), were studied by the electron paramagnetic resonance (EPR) method in the solid state. The sulfur rad...

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Bibliographic Details
Published in:Research on chemical intermediates 2009-04, Vol.35 (4), p.507-517
Main Authors: Strzelczak, Grazyna, Janeba-Bartoszewicz, Edyta, Carmichael, Ian, Marciniak, Bronislaw, Bobrowski, Krzysztof
Format: Article
Language:English
Subjects:
Catalysis
Chemistry
Chemistry and Materials Science
Inorganic Chemistry
Physical Chemistry
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Summary:Radicals formed in γ-irradiated 1,3,5-trithiane (TT) and its three derivatives, α- and β-2,4,6-trimethyl-1,3,5-trithiane (α-TMT and β-TMT), and 2,4,6-trimethyl-2,4,6-triphenyl-1,3,5-trithiane (TMTPT), were studied by the electron paramagnetic resonance (EPR) method in the solid state. The sulfur radical cations (>S +• ) were identified in all compounds at 77 K. In TT and its two derivatives, α-TMT and β-TMT, the >S +• decay via deprotonation-forming C-centered radicals. Further increase of temperature up to 293 K results in the appearance of thiyl-type radicals (RS • ). In TMTPT, the >S +• are stable up to 250 K. They formed the intermolecularly three-electron-bonded dimeric radical cations (S∴S) + while RS • radicals were not observed. Some of the radical assignments and their EPR parameters ( g and a hyperfine splittings) obtained support from the DFT calculations.
ISSN:0922-6168
1568-5675
DOI:10.1007/s11164-009-0054-4