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o is the initial concentration of the nucleophile; ArH and ArNu are the concentrations of the reduction and substitution products at time t. These equations are based on the assumption that the reactions of the aryl radicals with the nucleophiles and the solvent are first order in the latter species, and their concentrations are constant during the experiments.
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o is the initial concentration of the nucleophile; ArH and ArNu are the concentrations of the reduction and substitution products at time t. These equations are based on the assumption that the reactions of the aryl radicals with the nucleophiles and the solvent are first order in the latter species, and their concentrations are constant during the experiments.
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25
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c[S]).
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c["S"]).
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At a low and moderate sweep rate (0.05-1 V/s, Ep varied linearly with the logarithm of the sweep rate by 45 mV per unit on average with a peak width Ep/2, Ep, 65 mV on average. These values are typical of an EC mechanism with a mixed kinetic control by E (electron-transfer processes with the formation of the anion radical) and C (first-order cleavage of the anion radical) steps. From these electrochemical experiments, the reductive cleavage of 10b would follow a stepwise mechanism involving the intermediacy of the anion radical. For references, see: Andrieux, C. P, Le Gorande, A, Savèant, J. M. J. Am. Chem. Soc. 1992, 114, 6892-6904 and references cited therein
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p = 65 mV on average. These values are typical of an "EC" mechanism with a mixed kinetic control by E (electron-transfer processes with the formation of the anion radical) and C (first-order cleavage of the anion radical) steps. From these electrochemical experiments, the reductive cleavage of 10b would follow a stepwise mechanism involving the intermediacy of the anion radical. For references, see: Andrieux, C. P.; Le Gorande, A.; Savèant, J. M. J. Am. Chem. Soc. 1992, 114, 6892-6904 and references cited therein.
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a of MeCOSH should be 1 or 2 pK units higher than the value of PhCOSH.
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a of MeCOSH should be 1 or 2 pK units higher than the value of PhCOSH.
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35
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0000146752
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Borosky, G. L.; Pierini, A. B.; Rossi, R. A. J. Org. Chem. 1992, 57, 247-252.
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(a) Petrillo, G.; Novi, M.; Garbarino, G.; Filiberti, M. Tetrahedron 1989, 45, 7411-7420.
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(b) Petrillo, G.; Novi, M.; Garbarino, G.; Filiberti, M. Tetrahedron Lett. 1988, 29, 4185-4188.
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0033523263
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7 Whereas a change from concerted to stepwise was observed by changing the scan rate for PhI, PhBr and 1-iodonaphthalene follow a stepwise mechanism over the whole range of scan rate under electrochemical initiation. (a) Pause, L.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 1999, 121, 7158-7159.
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7 Whereas a change from concerted to stepwise was observed by changing the scan rate for PhI, PhBr and 1-iodonaphthalene follow a stepwise mechanism over the whole range of scan rate under electrochemical initiation. (a) Pause, L.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 1999, 121, 7158-7159.
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39
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0034741410
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On the other hand, despite the lower driving force exerted under homogeneous relative to that under electrochemical reduction, a stepwise mechanism has been proposed for the reduction of PhI by different radical anions. (b) Enemaerke, R. J.; Christensen, T. B.; Jensen, H.; Daasbjerg, K. J. Chem. Soc., Perkin Trans. 2001, 2, 1620-1630.
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On the other hand, despite the lower driving force exerted under homogeneous relative to that under electrochemical reduction, a stepwise mechanism has been proposed for the reduction of PhI by different radical anions. (b) Enemaerke, R. J.; Christensen, T. B.; Jensen, H.; Daasbjerg, K. J. Chem. Soc., Perkin Trans. 2001, 2, 1620-1630.
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33646361449
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-1. M'Halla, F.; Pinson, J.; Savéant, J.-M. J. Am. Chem. Soc. 1980, 102, 4120-4127.
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-1. M'Halla, F.; Pinson, J.; Savéant, J.-M. J. Am. Chem. Soc. 1980, 102, 4120-4127.
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(a) Annunziata, A.; Galli, C.; Marinelli, M.; Pau, T. Eur. J. Org. Chem. 2001, 1323-1329.
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Another possibility would be the formation of new radical anions by coupling of anions 1, 2, or 3 with radical 13, which are able to continue with the propagation cycle. The absence of chain propagation and the fact that not even traces of PhCOSCOPh were observed for anion 3 allow us to disregard this possibility.
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Another possibility would be the formation of new radical anions by coupling of anions 1, 2, or 3 with radical 13, which are able to continue with the propagation cycle. The absence of chain propagation and the fact that not even traces of PhCOSCOPh were observed for anion 3 allow us to disregard this possibility.
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0031049710
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Allongue, P.; Delamar, M.; Desbat, B.; Fagebaumme, O.; Hitmi, R.; Pinson, J.; Savéant, J.-M. J. Am. Chem. Soc. 1997, 119, 201-207.
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47
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34247214727
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When the reaction is performed with an excess of 1-bromonaphthalene, it was possible to observe 1-naphthalenethiol, acetate 10a, see ref 12, This clearly supports the competition between ET and fragmentation steps as shown in Scheme 5. Furthermore, if ArSCOMe was an intermediate in these reactions, we would be able to trap it by an intramolecular reaction with an amino or hydroxy group ortho to the leaving group. In the photoinduced reaction of o-amino-iodobenzene with thioacetate anion, followed by addition of MeI, the only products observed were ArSMe with the amino group mono- and di-methylated without any traces of the benzenethiazole derivative
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When the reaction is performed with an excess of 1-bromonaphthalene, it was possible to observe 1-naphthalenethiol, acetate (10a) (see ref 12). This clearly supports the competition between ET and fragmentation steps as shown in Scheme 5. Furthermore, if ArSCOMe was an intermediate in these reactions, we would be able to trap it by an intramolecular reaction with an amino or hydroxy group ortho to the leaving group. In the photoinduced reaction of o-amino-iodobenzene with thioacetate anion, followed by addition of MeI, the only products observed were ArSMe with the amino group mono- and di-methylated without any traces of the benzenethiazole derivative.
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48
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85051913106
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It should be emphasized that the relative value to 10b must be considered a lower limit in view of the preceding considerations. Therefore, the actual DGET0 value for the ET reaction with 1-bromonaphthalene should be larger than that reported in Table 4
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0 value for the ET reaction with 1-bromonaphthalene should be larger than that reported in Table 4.
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