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Volumn 114, Issue 9, 2014, Pages 5011-5056

Scavenging of organic C-centered radicals by nitroxides

Author keywords

[No Author keywords available]

Indexed keywords

FREE RADICAL; NITROGEN OXIDE; SCAVENGER;

EID: 84900455704     PISSN: 00092665     EISSN: 15206890     Source Type: Journal    
DOI: 10.1021/cr4000946     Document Type: Review
Times cited : (99)

References (280)
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    • Fremy's salt was the first nitroxide prepared
    • Fremy's salt was the first nitroxide prepared: Frémy, E. Ann. Chim. Phys. 1845, 15, 408.
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    • The first organic nitroxide porphyrexide was reported in 1901
    • The first organic nitroxide porphyrexide was reported in 1901: Piloty, O.; Schwerin, B. G. Ber. Dtsch. Chem. Ges. 1901, 34, 1870.
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    • The interest in this family blossomed with the preparation of the stable nitroxide N53 by Lebedev et al.
    • The interest in this family blossomed with the preparation of the stable nitroxide N53 by Lebedev et al.: Lebedev, O. L.; Khidekel, M. I.; Razuvaev, G. A. Dokl. Akad. Nauk SSSR 1961, 140, 1327.
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    • The IUPAC name for this family of molecules is aminoxyl radicals. However, the most common name "nitroxide" will be used throughout this review
    • The IUPAC name for this family of molecules is aminoxyl radicals. However, the most common name "nitroxide" will be used throughout this review.
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    • [Online]; Kokorin, A. I., Ed.; InTech: Rijeka, Croatia, (accessed 12/09/12)
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    • The solvent effect cannot always be estimated with high reliability
    • The solvent effect cannot always be estimated with high reliability.
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    • The first time-resolved experiment in an organic solvent was perfomed for the coupling of N1 and R13 although competitive conditions were still applied
    • The first time-resolved experiment in an organic solvent was perfomed for the coupling of N1 and R13 although competitive conditions were still applied: Johnston, L. J.; Scaiano, J. C.; Ingold, K. U. J. Am. Chem. Soc. 1984, 106, 4877.
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    • Other approaches rely on competition experiments; see refs 15 and 16
    • Other approaches rely on competition experiments; see refs 15 and 16.
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    • For an exhaustive compilation of kc measurements in water, see refs 15 and 16
    • For an exhaustive compilation of kc measurements in water, see refs 15 and 16.
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    • Nitroxides in synthetic radical chemistry
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    • As quoted by Fischer and Souaille
    • As quoted by Fischer and Souaille: Fischer, H.; Souaille, M. Macromol. Symp. 2001, 174, 231.
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    • In the absence of X-ray data for the nitroxide N11 and N12 family, the same conformation as for nitroxides N8-N10 was assumed
    • In the absence of X-ray data for the nitroxide N11 and N12 family, the same conformation as for nitroxides N8-N10 was assumed.
  • 120
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    • In general, dimerization can be observed for weakly congested nitroxides at low temperatures; see refs 113-115
    • In general, dimerization can be observed for weakly congested nitroxides at low temperatures; see refs 113-115.
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    • Nitroxides such as N95 and N96 are also prone to dimerization as well as to some other side reactions; see refs 34 and 116
    • Nitroxides such as N95 and N96 are also prone to dimerization as well as to some other side reactions; see refs 34 and 116.
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    • To the best of our knowledge, nobody reported the preparation of ketones or any other radical initiators carrying a polymer chain and suitable for the generation of polymeric radicals by photolysis. Moreover, no reports based on the approach developed in ref 51 involving polymers chains are available
    • To the best of our knowledge, nobody reported the preparation of ketones or any other radical initiators carrying a polymer chain and suitable for the generation of polymeric radicals by photolysis. Moreover, no reports based on the approach developed in ref 51 involving polymers chains are available.
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    • ?1 was ascribed to the principal fragment, i.e., ethyl group for primary C-centered radicals, isopropyl group for secondary C-centered radicals, and tert-butyl group for tertiary C-centered radicals. ?2 was ascribed to the function, and ?3 was ascribed to the penultimate group when required
    • ?1 was ascribed to the principal fragment, i.e., ethyl group for primary C-centered radicals, isopropyl group for secondary C-centered radicals, and tert-butyl group for tertiary C-centered radicals. ?2 was ascribed to the function, and ?3 was ascribed to the penultimate group when required.
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    • Carbon radicals with conjugated φ-system
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    • Nonconjugated carbon-centered radicals
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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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    • 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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    • Carbon radicals with conjugated φ-system
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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.
  • 211
    • 84900426155 scopus 로고    scopus 로고
    • 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.
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    • 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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    • 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.
  • 218
  • 219
    • 84900425157 scopus 로고    scopus 로고
    • 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.
  • 222
    • 84868379216 scopus 로고    scopus 로고
    • Some significant solvent effects on kd were recently reported for the homolysis of chemically activated alkoxyamines
    • Some significant solvent effects on kd were recently reported for the homolysis of chemically activated alkoxyamines: Audran, G.; Brémond, P.; Marque, S. R. A.; Obame, G. J. Org. Chem. 2012, 77 (21), 9634.
    • (2012) J. Org. Chem. , vol.77 , Issue.21 , pp. 9634
    • Audran, G.1    Brémond, P.2    Marque, S.R.A.3    Obame, G.4
  • 241
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    • Estimated with eqs 40-42
    • Estimated with eqs 40-42.
  • 242
    • 84900418005 scopus 로고    scopus 로고
    • 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 scopus 로고    scopus 로고
    • ? = 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 scopus 로고    scopus 로고
    • ? = 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 scopus 로고    scopus 로고
    • ? = 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
    • ? = 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.
  • 250
    • 78650626762 scopus 로고    scopus 로고
    • A general discussion of the various types of HAT is provided by Warren et al.
    • A general discussion of the various types of HAT is provided by Warren et al.: Warren, J. J.; Tronic, T. A.; Mayer, J. M. Chem. Rev. 2010, 110, 6961.
    • (2010) Chem. Rev. , vol.110 , pp. 6961
    • Warren, J.J.1    Tronic, T.A.2    Mayer, J.M.3
  • 274
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    • Calculations on the thermodynamics of the homolysis reaction were first performed by Georges et al. and Kysel et al.
    • Calculations on the thermodynamics of the homolysis reaction were first performed by Georges et al. and Kysel et al.: Georges, M. K.; Veregin, R. P. N.; Kazmaier, P. M.; Hamer, G. K. Trends Polym. Sci. 1993, 2, 66.
    • (1993) Trends Polym. Sci. , vol.2 , pp. 66
    • Georges, M.K.1    Veregin, R.P.N.2    Kazmaier, P.M.3    Hamer, G.K.4


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