Transients in the oxidative and H-atom-induced degradation of 1,3,5-trithiane. Time-resolved studies in aqueous solution.

The ()OH-induced oxidation of 1,3,5-trithiacyclohexane (1) in aqueous solution was studied by means of pulse radiolysis with optical and conductivity detection. This oxidation leads, via a short-lived ()OH radical adduct (<1 micros), to the radical cation 1(+) showing a broad absorption with lambda(max) equal to 610 nm. A defined pathway of the decay of 1(+) is proton elimination. It occurs with k = (2.2 +/- 0.2) x 10(4) s(-1) and yields the cyclic C-centered radical 1(-H)(). The latter radical decays via ring opening (beta-scission) with an estimated rate constant of about 10(5) s(-1). A distinct, immediate product (formed with the same rate constant) is characterized by a narrow absorption band with lambda(max) = 310 nm and is attributed to the presence of a dithioester function. The formation of the 310 nm absorption can be suppressed in the presence of oxygen, the rationale for this being a reaction of the C-centered cyclic radical 1(-H)() with O(2). The disappearance of the 310 nm band (with a rate constant of 900 s(-1)) is associated with the hydrolysis of the dithioester functionality. A further aspect of this study deals with the reaction of H() atoms with 1 which yields a strongly absorbing, three-electron-bonded 2sigma/1sigma radical cation 1(S therefore S)-H (lambda(max) = 400 nm). Its formation is based on an addition of H() to one of the sulfur atoms, followed by beta-scission, intramolecular sulfur-sulfur coupling (constituting a ring contraction), and further stabilization of the S therefore S bond thus formed by protonation. 1(S therefore S)-H decays with a first-order rate constant of about 10(4) s(-1). Its formation can be suppressed by the addition of oxygen which scavenges the H() atoms prior to their reaction with 1. Complementary time-resolved conductivity experiments have provided information on the quantification of the 1(*+) radical cation yield, the cationic longer-lived follow-up species, extinction coefficients, and kinetics concerning deprotonation processes as well as further reaction steps after hydrolysis of the transient dithioesters. The results are also discussed in the light of previous photochemical studies.