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EnglishThe reaction between NO3' and polyalkylbenzenes was studied using 308-nm laser flash photolysis of cerium- (IV) ammonium nitrate in the presence of the alkylbenzenes in acetonitrile solution. For all benzenes, with the exception of monoalkylbenzenes and 0- and m-xylene, the reaction with NO3* was found to yield the corresponding radical cations and to proceed in an apparently straightforward bimolecular manner. For monoalkylbenzenes and 0- and m-xylene, radicals were seen which are derived from the parents by formal loss of H' from the side chain of the aromatic. This reaction proceeds via a complex between the aromatic and NO,' with the decomposition of the complex being rate determining at higher concentrations of aromatic (rate constants for decomposition between 6 X IO5 and 4 X lo7 s-l). In the complex, electron transfer from the aromatic to NO3* is suggested to be concerted with deprotonation of the incipient radical cation. Formation of a complex between NO3* and aromatic is likely even in those cases where radical cations are observed, with the assumption that in these cases the complex decomposition rate is 16 X lo7 s-l.
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| Titolo: | One-electron oxidation of alkylbenzenes in acetonitrile by photochemically produced nitrate radical: evidence for an inner-sphere mechanism |
| Autori: | |
| Data di pubblicazione: | 1993 |
| Rivista: | |
| Abstract: | The reaction between NO3' and polyalkylbenzenes was studied using 308-nm laser flash photolysis of cerium- (IV) ammonium nitrate in the presence of the alkylbenzenes in acetonitrile solution. For all benzenes, with the exception of monoalkylbenzenes and 0- and m-xylene, the reaction with NO3* was found to yield the corresponding radical cations and to proceed in an apparently straightforward bimolecular manner. For monoalkylbenzenes and 0- and m-xylene, radicals were seen which are derived from the parents by formal loss of H' from the side chain of the aromatic. This reaction proceeds via a complex between the aromatic and NO,' with the decomposition of the complex being rate determining at higher concentrations of aromatic (rate constants for decomposition between 6 X IO5 and 4 X lo7 s-l). In the complex, electron transfer from the aromatic to NO3* is suggested to be concerted with deprotonation of the incipient radical cation. Formation of a complex between NO3* and aromatic is likely even in those cases where radical cations are observed, with the assumption that in these cases the complex decomposition rate is 16 X lo7 s-l. |
| Handle: | http://hdl.handle.net/11391/922687 |
| Appare nelle tipologie: | 1.1 Articolo in rivista |
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