2010
DOI: 10.1016/j.jphotochem.2010.01.005
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Participation of a heterolytic path in the photochemistry of chlorobenzene

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Cited by 14 publications
(22 citation statements)
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“…1A). Chlorinated arenes (like LTG's dichlorophenyl ring) have been observed to undergo photochemical reactions through excited state charge transfer complexes, 50 and there is at least some potential for LTG 0 and LTG + to form ground state complexes via cation-p bond interactions, 51 but the LTG concentrations used in this study are low (<0.05 mM), and LTG concentrations in the environment are even lower. It is more likely that the reaction quantum yields in Table 1 are affected by small errors in determining the solar simulator's spectral irradiance or LTG's molar absorptivity, particularly at pH 3.3 and 5.3 where their spectral overlap is small (Fig.…”
Section: Direct Photodegradation Rates and Reaction Quantum Yieldsmentioning
confidence: 82%
“…1A). Chlorinated arenes (like LTG's dichlorophenyl ring) have been observed to undergo photochemical reactions through excited state charge transfer complexes, 50 and there is at least some potential for LTG 0 and LTG + to form ground state complexes via cation-p bond interactions, 51 but the LTG concentrations used in this study are low (<0.05 mM), and LTG concentrations in the environment are even lower. It is more likely that the reaction quantum yields in Table 1 are affected by small errors in determining the solar simulator's spectral irradiance or LTG's molar absorptivity, particularly at pH 3.3 and 5.3 where their spectral overlap is small (Fig.…”
Section: Direct Photodegradation Rates and Reaction Quantum Yieldsmentioning
confidence: 82%
“…Furthermore, the products of the reaction with allyltrimethylsilane and those with hexamethylbenzene are typical markers of a triplet aryl cation and are best rationalized as resulting from electron transfer (ET) within the thienyl and halogen radical pair [ 14 • X • ] 3 . This leads indirectly to ion 3 14 + (Scheme , path g) , which is trapped by π-bond nucleophiles to give the arylated products (path h). The formation of aryl cations from an ET mechanism within a radical pair has been sparsely documented, providing that it takes place in a high polar medium (e.g., water). ,, Notice further that 5-uracyl and 5-citosyl cations have been invoked when investigating the reactivity of 5-fluorouracil and 5-bromocytosine, respectively, where the heteroaryl radical intermediate was oxidized by the radical cation of N α -acetyl- l -tryptophan N -ethylamide. , More relevant to the present case, the formation of the parent triplet phenyl cation from the corresponding aryl radical has been previously postulated in the photodechlorination of chlorobenzene .…”
Section: Discussionmentioning
confidence: 99%
“…This leads indirectly to ion 3 14 + (Scheme , path g) , which is trapped by π-bond nucleophiles to give the arylated products (path h). The formation of aryl cations from an ET mechanism within a radical pair has been sparsely documented, providing that it takes place in a high polar medium (e.g., water). ,, Notice further that 5-uracyl and 5-citosyl cations have been invoked when investigating the reactivity of 5-fluorouracil and 5-bromocytosine, respectively, where the heteroaryl radical intermediate was oxidized by the radical cation of N α -acetyl- l -tryptophan N -ethylamide. , More relevant to the present case, the formation of the parent triplet phenyl cation from the corresponding aryl radical has been previously postulated in the photodechlorination of chlorobenzene . The formation of a small amount of trifluoroethoxythiophene ( 2e′ ) in TFE is best justified via ISC from triplet to singlet thienyl cation ( 1 14 + , Scheme , path i) .…”
Section: Discussionmentioning
confidence: 99%
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