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-
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84900402797
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It was assumed that the 1,4-dihydronaphthalen-1-yl radical is a suitable model for R22
-
It was assumed that the 1,4-dihydronaphthalen-1-yl radical is a suitable model for R22.
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84985386347
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84900454037
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In ref 163, Fischer and co-workers noted that the steric effect was anticorrelated to the effect observed for the homolysis
-
In ref 163, Fischer and co-workers noted that the steric effect was anticorrelated to the effect observed for the homolysis.
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84900421800
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The 13C hyperfine coupling constant for 100% s character in the SOMO is given as a13C(2s) = 113.0 mT
-
The 13C hyperfine coupling constant for 100% s character in the SOMO is given as a13C(2s) = 113.0 mT.
-
-
-
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210
-
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84900431744
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Fischer, H., Ed.; Landolt-Börnstein, Group II; Springer-Verlag: Berlin, See also ref 195
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Fischer, H.1
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211
-
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84900426155
-
-
Assuming a 13C hyperfine coupling constant for the radical anion of 2,2,4,4-tetramethylcyclobutanol suitable for R14, a13C = 5.02 mT, and affording 4.4% s character in the SOMO. Assuming a 13C hyperfine coupling constant for the radical anion of 2,2,5,5- tetramethylcyclopentanol suitable for R15, a13C = 4.39 mT, and affording 3.9% s character in the SOMO. See refs 205 and 206
-
Assuming a 13C hyperfine coupling constant for the radical anion of 2,2,4,4-tetramethylcyclobutanol suitable for R14, a13C = 5.02 mT, and affording 4.4% s character in the SOMO. Assuming a 13C hyperfine coupling constant for the radical anion of 2,2,5,5- tetramethylcyclopentanol suitable for R15, a13C = 4.39 mT, and affording 3.9% s character in the SOMO. See refs 205 and 206.
-
-
-
-
213
-
-
84900452461
-
-
It is important to mention that σRS was developed only for planar (sp2-hybridized) C-centered radicals. Therefore, heteroatomcentered radicals H1-H6 were not included in the correlations. Although the hybridization of the alkyl radical center of R13 and R14 was different from the sp2 hybridization needed to estimate RSE, these radicals were included in the correlation because their RSE is not likely to be smaller than that of the Me radical and it should roughly obey the procedures set to estimate RSE for primary, secondary, and tertiary C-centered radicals. See ref 194
-
It is important to mention that σRS was developed only for planar (sp2-hybridized) C-centered radicals. Therefore, heteroatomcentered radicals H1-H6 were not included in the correlations. Although the hybridization of the alkyl radical center of R13 and R14 was different from the sp2 hybridization needed to estimate RSE, these radicals were included in the correlation because their RSE is not likely to be smaller than that of the Me radical and it should roughly obey the procedures set to estimate RSE for primary, secondary, and tertiary C-centered radicals. See ref 194.
-
-
-
-
215
-
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84900442507
-
-
The presence of an EWG attached to the radical center, i.e., increasing the polarity, is expected to destabilize the C-centered radical and, consequently, to increase the spin density on the radical center. Hence, it would be ascribed to an enthalpic effect. However, it is likely that such an effect on the distribution of spin density is already described by the stabilization parameter σRS
-
The presence of an EWG attached to the radical center, i.e., increasing the polarity, is expected to destabilize the C-centered radical and, consequently, to increase the spin density on the radical center. Hence, it would be ascribed to an enthalpic effect. However, it is likely that such an effect on the distribution of spin density is already described by the stabilization parameter σRS.
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The phenyl group is known as a Janus group; that is, it can adopt many conformations, implying several possible values of Es,Ph. See refs 32, 155, 156, 216, and 217
-
The phenyl group is known as a Janus group; that is, it can adopt many conformations, implying several possible values of Es,Ph. See refs 32, 155, 156, 216, and 217.
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222
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84868379216
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Some significant solvent effects on kd were recently reported for the homolysis of chemically activated alkoxyamines
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241
-
-
84900450930
-
-
Estimated with eqs 40-42
-
Estimated with eqs 40-42.
-
-
-
-
242
-
-
84900418005
-
-
S = styrene or styryl fragment, BA = n-butyl acrylate of nbutylacrylyl fragment, and MMA = methyl methacrylate or methylmethacrylyl fragment
-
S = styrene or styryl fragment, BA = n-butyl acrylate of nbutylacrylyl fragment, and MMA = methyl methacrylate or methylmethacrylyl fragment.
-
-
-
-
243
-
-
84900415265
-
-
? = 1.24, σI = 0.05, σRS = 0.34, ?1 = ?i?Pr = 0.76, ?2 = ?CHMePh = 0.99, ?3 = ?Ph = 0.57,a nd σI,CH2CHPhMe = 0.02. It was assumed that the penultimate unit had no effect on the radical stabilization
-
? = 1.24, σI = 0.05, σRS = 0.34, ?1 = ?i?Pr = 0.76, ?2 = ?CHMePh = 0.99, ?3 = ?Ph = 0.57,a nd σI,CH2CHPhMe = 0.02. It was assumed that the penultimate unit had no effect on the radical stabilization.
-
-
-
-
244
-
-
84900420098
-
-
? = 1.37, σI = 0.11, σRS = 0.18, ?1 = ?i?Pr = 0.76, ?2 = ?CHMeCOOMe = 1.01, ?3 = ?COOMe = 0.9, and σI,CH2CHMeCOOMe = 0.03. It was assumed that the penultimate unit had no effect on the radical stabilization
-
? = 1.37, σI = 0.11, σRS = 0.18, ?1 = ?i?Pr = 0.76, ?2 = ?CHMeCOOMe = 1.01, ?3 = ?COOMe = 0.9, and σI,CH2CHMeCOOMe = 0.03. It was assumed that the penultimate unit had no effect on the radical stabilization.
-
-
-
-
245
-
-
84900435112
-
-
? = 1.96, σI = 0.09, σRS = 0.20, ?1 = ?t?Bu = 1.24, ?2 = ?CMe2COOMe = 1.43, ?3 = ?COOMe = 0.9, and σI,CH2CMe2COOMe = 0.02. It was assumed that the penultimate unit had no effect on the radical stabilization
-
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