Direct Irradiaton of Aryl Sulfides: Homolytic Fragmentation and Sensitized S-Oxidation
The direct irradiation of diphenyl sulfide and p-substituted thioanisoles in the presence of oxygen was investigated by means of both steady state and laser flash photolysis experiments. Two competitive pathways took place from the triplet excited state of thioanisoles, C-S bond cleavage, finally le...
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2017
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| Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v82_n17_p9054_Bonesi http://hdl.handle.net/20.500.12110/paper_00223263_v82_n17_p9054_Bonesi |
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paper:paper_00223263_v82_n17_p9054_Bonesi2025-07-30T17:31:38Z Direct Irradiaton of Aryl Sulfides: Homolytic Fragmentation and Sensitized S-Oxidation Chemical bonds Excited states Oxidation Photolysis Rate constants Sulfur compounds C-S bond cleavage Diphenyl sulfoxides Direct irradiation Dodecyl methyl sulfide Laser flash photolysis Radical cations Sensitized oxidation Time resolved experiments Reaction intermediates biphenyl diphenyl sulfoxide singlet oxygen sulfoxide unclassified drug Article chemical bond chemical structure electron transport irradiation photochemistry photooxidation quantum yield steady state The direct irradiation of diphenyl sulfide and p-substituted thioanisoles in the presence of oxygen was investigated by means of both steady state and laser flash photolysis experiments. Two competitive pathways took place from the triplet excited state of thioanisoles, C-S bond cleavage, finally leading to aryl sulfinic acid and sensitized oxidation leading to S-oxidation. Co-oxidation of dodecyl methyl sulfide occurred efficiently implying that an S-persulfoxide intermediate is involved during the sensitized oxidation. On the other hand, triplet state of diphenyl sulfide also showed competitive C-S bond cleavage giving phenyl sulfinic acid and ionization to diphenyl sulfide radical cation that in turn led to diphenyl sulfoxide. The rate constants of the above reactions were determined by time-resolved experiments. © 2017 American Chemical Society. 2017 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v82_n17_p9054_Bonesi http://hdl.handle.net/20.500.12110/paper_00223263_v82_n17_p9054_Bonesi |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Chemical bonds Excited states Oxidation Photolysis Rate constants Sulfur compounds C-S bond cleavage Diphenyl sulfoxides Direct irradiation Dodecyl methyl sulfide Laser flash photolysis Radical cations Sensitized oxidation Time resolved experiments Reaction intermediates biphenyl diphenyl sulfoxide singlet oxygen sulfoxide unclassified drug Article chemical bond chemical structure electron transport irradiation photochemistry photooxidation quantum yield steady state |
| spellingShingle |
Chemical bonds Excited states Oxidation Photolysis Rate constants Sulfur compounds C-S bond cleavage Diphenyl sulfoxides Direct irradiation Dodecyl methyl sulfide Laser flash photolysis Radical cations Sensitized oxidation Time resolved experiments Reaction intermediates biphenyl diphenyl sulfoxide singlet oxygen sulfoxide unclassified drug Article chemical bond chemical structure electron transport irradiation photochemistry photooxidation quantum yield steady state Direct Irradiaton of Aryl Sulfides: Homolytic Fragmentation and Sensitized S-Oxidation |
| topic_facet |
Chemical bonds Excited states Oxidation Photolysis Rate constants Sulfur compounds C-S bond cleavage Diphenyl sulfoxides Direct irradiation Dodecyl methyl sulfide Laser flash photolysis Radical cations Sensitized oxidation Time resolved experiments Reaction intermediates biphenyl diphenyl sulfoxide singlet oxygen sulfoxide unclassified drug Article chemical bond chemical structure electron transport irradiation photochemistry photooxidation quantum yield steady state |
| description |
The direct irradiation of diphenyl sulfide and p-substituted thioanisoles in the presence of oxygen was investigated by means of both steady state and laser flash photolysis experiments. Two competitive pathways took place from the triplet excited state of thioanisoles, C-S bond cleavage, finally leading to aryl sulfinic acid and sensitized oxidation leading to S-oxidation. Co-oxidation of dodecyl methyl sulfide occurred efficiently implying that an S-persulfoxide intermediate is involved during the sensitized oxidation. On the other hand, triplet state of diphenyl sulfide also showed competitive C-S bond cleavage giving phenyl sulfinic acid and ionization to diphenyl sulfide radical cation that in turn led to diphenyl sulfoxide. The rate constants of the above reactions were determined by time-resolved experiments. © 2017 American Chemical Society. |
| title |
Direct Irradiaton of Aryl Sulfides: Homolytic Fragmentation and Sensitized S-Oxidation |
| title_short |
Direct Irradiaton of Aryl Sulfides: Homolytic Fragmentation and Sensitized S-Oxidation |
| title_full |
Direct Irradiaton of Aryl Sulfides: Homolytic Fragmentation and Sensitized S-Oxidation |
| title_fullStr |
Direct Irradiaton of Aryl Sulfides: Homolytic Fragmentation and Sensitized S-Oxidation |
| title_full_unstemmed |
Direct Irradiaton of Aryl Sulfides: Homolytic Fragmentation and Sensitized S-Oxidation |
| title_sort |
direct irradiaton of aryl sulfides: homolytic fragmentation and sensitized s-oxidation |
| publishDate |
2017 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v82_n17_p9054_Bonesi http://hdl.handle.net/20.500.12110/paper_00223263_v82_n17_p9054_Bonesi |
| _version_ |
1840324028351381504 |