66729-81-5Relevant academic research and scientific papers
Phenylsulfinyl Radical: Gas-Phase Generation, Photoisomerization, and Oxidation
Xu, Jian,Wu, Zhuang,Wan, Huabin,Deng, Guohai,Lu, Bo,Eckhardt, André K.,Schreiner, Peter R.,Trabelsi, Tarek,Francisco, Joseph S.,Zeng, Xiaoqing
, p. 9972 - 9978 (2018/07/21)
Arylsulfinyl radicals are key intermediates in sulfoxide chemistry. The parent molecule, phenylsulfinyl radical PhSOa€￠, has been generated for the first time in the gas phase through high-vacuum flash pyrolysis of PhS(O)R (R = CF3 and Cl) at a
Quenching of singlet oxygen by oxygen- and sulfur-centered radicals: Evidence for energy transfer to peroxyl radicals in solution
Darmanyan, Alexandre P.,Gregory, Daniel D.,Guo, Yushen,Jenks, William S.,Burel, Laure,Eloy, Dominique,Jardon, Pierre
, p. 396 - 403 (2007/10/03)
Quenching of singlet oxygen luminescence at 1.27 μm by PhS., PhSO., and peroxyl radicals PhOO., t-BuOO., PhCH2OO., Ph2CHOO. and Ph3COO. was studied in liquid solution. The quantum yields of decomposition of different initiators which lead to the formation of free radicals were measured by using nanosecond transient absorption. This allowed determination of singlet oxygen O2(1Δ(g)) quenching rate constants by the radicals. They are 8 M-1 s-1 for the sulfur-centered radicals and (2-7) x 109 M-1 s-1 for peroxyl radicals in acetonitrile. The rapid quenching is attributed to energy transfer quenching by the peroxyls, which have an n → π* transition leading to a low-lying 2A' state above their 2A'' ground state. PhSO. is shown computationally not to have such a low-lying 2A' state. There may be a very low-lying 2B1 state, for PhS., but it is apparently not an efficient acceptor of electronic energy from O2(1Δ(g)).
Post-irradiation Decomposition of Sulfanylperoxides and Peroxycyclohexadienethiones formed from Thiyl and Peroxyl Radicals
Mile, Brynmor,Rowlands, Christopher C.,Sillman, Philip D.,Holmes, Andrew J.
, p. 2141 - 2148 (2007/10/02)
Photolysis of (E)-azoisobutane and dialkyl and diaryl disulfides in oxygenated 2-methylbutane at temperatures below 230 K results in a very low photostationary state of peroxyl radical, because of the high efficiency of the mixed termination reaction to form sulfanylperoxide and peroxycyclohexadienethione.Surprisingly, after photolysis is stopped there is an immediate threefold rise in the peroxyl radical concentration.This post-illumination dark reaction is interpreted and accurately modelled using an algorithm, by assuming an irreversible decomposition of the sulfanylperoxide or peroxycyclohexadienethione to alkoxyl and other radicals.Spin traps have been used to confirm the nature of the radicals involved in many of the proposed reactions and to give a measure of radical concentrations under various experimental conditions.Values of the rate parameters for a number of these reactions have been measured and Arrhenius parameters E2 = 34 kJ mol-1, A2 = 106 s-1, E2 = 14 kJ mol-1, A2 = 102.4 s-1 determined for the decomposition of phenyl and tert-butyl sulfanylperoxides, respectively.The low A factor for tert-butyl sulfonylperoxide is probably associated with a tight, four-membered ring transition state with a loss of internal rotations about partially formed sulfur-oxygen double bonds and accompanying solvent orientations about the more dipolar S=O bond.The decomposition of the phenyl analogue occurs by scission of O-O links in para and ortho substituted peroxycyclohexadienethione.
