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A sulfide radical cation can also undergo C-S bond cleavage giving a sulfenyl cation and an alkyl radical, but as far as we know, there is no report dealing with this type of cleavage that generally is less thermodynamically favored with respect to that reported in eq 1
-
A sulfide radical cation can also undergo C-S bond cleavage giving a sulfenyl cation and an alkyl radical, but as far as we know, there is no report dealing with this type of cleavage that generally is less thermodynamically favored with respect to that reported in eq 1.
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The C-S cleavage occurs by a unimolecular pathway as demonstrated by the study of the stereochemistry of the C-S fragmentation in 1-phenylethyl phenyl sulfide radical cation. (10)
-
The C-S cleavage occurs by a unimolecular pathway as demonstrated by the study of the stereochemistry of the C-S fragmentation in 1-phenylethyl phenyl sulfide radical cation. (10)
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84855638371
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3CN used in all of the experiments
-
3CN used in all of the experiments
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55
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37049089323
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max value (580 nm) has been reported for the radical cation of 4-methoxythioanisole in water
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-
-
84855634790
-
-
1/2 = 7.3 μs
-
1/2 = 7.3 μs.
-
-
-
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58
-
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84855638367
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-
+
-
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73
-
-
84855633784
-
-
+ • with respect to the a conformers (see Table S2 in Supporting Information)
-
+ • with respect to the a conformers (see Table S2 in Supporting Information).
-
-
-
-
74
-
-
84855633786
-
-
+•
-
+•.
-
-
-
-
75
-
-
84855633785
-
-
+ •. The two barriers were found to be very low: 1.97 and 0.52 kcal/mol for the a → b and b → a conversion, respectively. Therefore it should no matter if the radical cation is predominantly formed in conformation a when this is the most stable conformation
-
+ •. The two barriers were found to be very low: 1.97 and 0.52 kcal/mol for the a → b and b → a conversion, respectively. Therefore it should no matter if the radical cation is predominantly formed in conformation a when this is the most stable conformation.
-
-
-
-
79
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77952971409
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Jurić, S.1
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-
80
-
-
84855633780
-
-
+ ≈ -4.5 for substituted tert -cumyl chlorides (40))
-
+ ≈ -4.5 for substituted tert -cumyl chlorides (40)).
-
-
-
-
81
-
-
0011493194
-
-
Okamoto, Y.; Inukai, T.; Brown, H. C. J. Am. Chem. Soc. 1958, 80, 4972-4976
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Okamoto, Y.1
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82
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33751138998
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Maslak, P.; Vallombroso, T. M.; Chapman, W. H.; Narvaez, J. N. Angew. Chem., Int. Ed. Engl. 1994, 33, 73-75
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-
Maslak, P.1
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Narvaez, J.N.4
-
83
-
-
78651511457
-
-
note
-
-1 more endergonic than C-S bond cleavage.
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