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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Citations
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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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Journal ArticleDOI
Thermodynamics of S.˙.S 2σ/1σ* Three-electron Bonds and Deprotonation Kinetics of Thioether Radical Cations in Aqueous Solution
J. Mönig,R. Goslich,K.-D. Asmus +2 more
TL;DR: In this paper, a time-resolved pulse radiolysis study has been carried out on the R2S+· R 2S ⇆ (R2S.˙.SR2)+ equilibrium and associated decay kinetics of sulfur centered radical cations.
Journal ArticleDOI
Three electron bonds. I. The H2SSH radical cation
TL;DR: In this article, the performance of MNDO semi-empirical molecular orbital theory is compared with the ab initio results for H2S, its radical cation, and the H2SSH radicalcation.
Journal ArticleDOI
Free radical oxidation of organic sulphur compounds in aqueous solution
TL;DR: In this article, a 3-electron-through-space-bond between two sulphur atoms of the same molecule is established and absorption maxima are red shifted to ≥600 nm.
Journal ArticleDOI
Unstable intermediates. Part 179. Electron spin resonance studies of radicals formed in irradiated organic sulphides and disulphides
TL;DR: In this article, the reaction R2S˙++R2S → R2s−SR2+ is considered and it is suggested that certain species, previously identified as R2 s˙+, are better identified as r2 s−SR 2+.
Journal ArticleDOI
Pulse radiolysis generation of sulfur radical cations stabilized by neighboring carboxylate and alcohol groups
Richard S. Glass,Massoud Hojjatie,George S. Wilson,Sabine Mahling,Manfred Goebl,Klaus Dieter Asmus +5 more
TL;DR: In this paper, the results of the pulse radiolytic generation of radical cations derived from dialkyl thioethers were described, including carboxylate and alcohol groups.