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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Autores principales: Bonesi, S.M., Crespi, S., Merli, D., Manet, I., Albini, A.
Formato: JOUR
Materias:
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
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_00223263_v82_n17_p9054_Bonesi
Aporte de:
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id todo:paper_00223263_v82_n17_p9054_Bonesi
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spelling todo:paper_00223263_v82_n17_p9054_Bonesi2023-10-03T14:31:31Z Direct Irradiaton of Aryl Sulfides: Homolytic Fragmentation and Sensitized S-Oxidation Bonesi, S.M. Crespi, S. Merli, D. Manet, I. Albini, A. 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. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar 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
Bonesi, S.M.
Crespi, S.
Merli, D.
Manet, I.
Albini, A.
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.
format JOUR
author Bonesi, S.M.
Crespi, S.
Merli, D.
Manet, I.
Albini, A.
author_facet Bonesi, S.M.
Crespi, S.
Merli, D.
Manet, I.
Albini, A.
author_sort Bonesi, S.M.
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
url http://hdl.handle.net/20.500.12110/paper_00223263_v82_n17_p9054_Bonesi
work_keys_str_mv AT bonesism directirradiatonofarylsulfideshomolyticfragmentationandsensitizedsoxidation
AT crespis directirradiatonofarylsulfideshomolyticfragmentationandsensitizedsoxidation
AT merlid directirradiatonofarylsulfideshomolyticfragmentationandsensitizedsoxidation
AT maneti directirradiatonofarylsulfideshomolyticfragmentationandsensitizedsoxidation
AT albinia directirradiatonofarylsulfideshomolyticfragmentationandsensitizedsoxidation
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