Book ChapterDOI
Sulfur-Centered Three-Electron Bonded Radical Species
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In this article, it was shown that if one of the antibonding σ* electrons is removed, the electronic σ/σ* configuration would be a slight repulsion of the two atoms.Abstract:
We all know that it is not possible to stabilize a He2 molecule. Any interaction of the filled He is orbitals would lead to the establishment of bonding a and antibonding σ* energy levels, both doubly occupied. As σ*, for quantum mechanical reasons, is raised a little bit more than σ is lowered relative to the original atomic energy levels the net result of this electronic σ/σ* configuration would be a slight repulsion of the two atoms. The situation becomes significantly different though if one of the antibonding σ* electrons is removed.
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Electron Transfer and Singlet Oxygen Mechanisms in the Photooxygenation of Dibutyl Sulfide and Thioanisole in MeCN Sensitized by N-Methylquinolinium Tetrafluoborate and 9,10-Dicyanoanthracene. The Probable Involvement of a Thiadioxirane Intermediate in Electron Transfer Photooxygenations
Enrico Baciocchi,Tiziana Del Giacco,Fausto Elisei,Maria Francesca Gerini,Maurizio Guerra,and Andrea Lapi,Prisca Liberali +6 more
TL;DR: It was conclusively shown that with both sensitizers, the photooxygenations of PhSMe occur by an electron transfer (ET) mechanism, as no sulfoxidation was observed in the presence of benzoquinone (BQ), which is a trap for O2-*, NMQ*, and DCA-*.
Journal ArticleDOI
Radical Cations in the OH-Radical-Induced Oxidation of Thiourea and Tetramethylthiourea in Aqueous Solution
WF（王文峰） Wang,Man Nien Schuchmann,Heinz-Peter Schuchmann,W. Knolle,J. von Sonntag,C. von Sonntag +5 more
TL;DR: Hydroxyl radicals were generated radiolytically in N(2)O-saturated aqueous solutions of thiourea and tetramethylthiou Andrea and it has been shown that, in both cases, OH(-) and a positively charged species are produced.
Journal ArticleDOI
Oxidation of thiourea and substituted thioureas: a review
TL;DR: In this paper, a review of the synthetic aspects and mechanism/schemes of the reactions discussed in the manuscript are based on stoichiometry and products of the reaction reactions and the reaction conditions and types of oxidants steer the formation of different products.
Journal ArticleDOI
Free-radical repair by a novel perthiol: reversible hydrogen transfer and perthiyl radical formation
TL;DR: The thermodynamic driving force for the observed enhanced free-radical repair reactivity of RSSH compared to RSH is attributed to the resonance stabilization energy of 8.8 kJ mol-1 within the RSS.
Book ChapterDOI
Sulfur Radical Cations
TL;DR: Sulfur radical cations are novel reaction intermediates that have attracted considerable attention recently as mentioned in this paper, in part due to renewed interest in the chemistry of sulfur cations in general, as well as four other factors.
References
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Formation of positive ions and other primary species in the oxidation of sulphides by hydroxyl radicals
TL;DR: The first step is addition of the OH· to sulphur to form R2ṠOH radicals, and the stable oxidation product, sulphoxide, has been identified as discussed by the authors.
Journal ArticleDOI
An investigation of mesocyclic and acyclic dithioether cation radicals and dications
Journal ArticleDOI
Substituent effects on the stability of three-electron-bonded radicals and radical ions from organic sulfur compounds
TL;DR: Effet des substituants inducteurs d'electrons R sur la stabilite de (R 2 S...SR 2 ) +, (RS...SR) − et R 2 S...B 2. L'etude est faite par radiolyse pulsee as mentioned in this paper.
Journal ArticleDOI
Structure and stability of radical cations from cyclic and open-chain dithia compounds in aqueous solutions. [Pulsed irradiation]
TL;DR: In this article, the formation of radical cation complexes has been observed during the oxidation of cyclic and open-chain organic dithia compounds (the two S atoms not adjacent) by hydroxyl radicals in aqueous solutions, and a new sulfur-sulfur bond established by interaction of the unpaired p electron from the oxidized sulfur atom with the free p-electron pair of a second sulfur atom.
Journal ArticleDOI
Long-lived radical cations from mesocyclic dithioethers
W. K. Musker,T. L. Wolford +1 more