Journal of Physical Chemistry p. 4417 - 4422 (1982)
Update date:2022-08-29
Topics:
Wu, Zhennan
Back, Thomas G.
Ahmad, Rizwan
Yamdagni, Raghav
Armstrong, David A.
Each of the of the reducing radicals eaq., .CO2- and (CH3)2.COH cleaves bis(2-hydroxyethyl) trisulfide in aqueous solution to produce (2-hydroxyethyl)perthiyl (RSS.) radicals and 2-hydroxyethanethiol.The RSS. radical had λmax = 374 nm, εmax = 1630 +/- 50 M-1cm-1, and a second-order rate constant for dimerization 2k12 = (1.4 +/- 0.3)*109 M-1s-1 (2RSS. -> RS4R (12)).It is able to abstract H atoms from dihydroflavin adenine dinucleotide (FH2), but not from formate.Thus, in aqueous solution DRSS-H must be greater than 60 but less than 90 kcal/mol.Although tetrasulfide and thiol are initial products of reduction, secondary thermal reactions occur and produce sulfanes (RSnH) and polysulfides (RSnR).In the early stages of reduction products of n = 2 dominate.However, on prolonged reaction with .CO2- elemental sulfur precipitated, and this is probably formed by elimination from sulfanes with n much larger and in the region of 8.
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