- Electron Loss from 1,3,3-Trimethyl-2-azabicyclooctane Derivatives. Is ? Coupling Thermodynamically Important?
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The ease of one-electron oxidation is compared for ? coupled and non-?-coupled γ-oxopiperidine nitroxides and their saturated analogues (CO -> CH2).For the non-?-coupled pair, 1,3,3-trimethyl-2-oxyl-2-azabicyclooctan-5-one (9) has IPv = 7.29 eV, Eo' = 0.73 V and its CO -> CH2 analogue 11 IPv = 6.88, Eo' = 0.52 V.The ?-coupled pair 9-oxyl-9-azabicyclononan-3-one (12) has IPv = 7.78 eV, Eo' = 0.83 V and its CO -> CH2 analogue 13 IPv = 7.39 eV, Eo' = 0.58 V.Replacement of CO by CH2 in the non-?-coupled example has as large an effectof IPv and only a 13percent smaller effect on Eo' than in the ?-coupled example, making it appear that a ?-coupled transmission of positive charge from the nitrogen to the carbonyl in the radical cation is unimportant.
- Nelsen, Stephen F.,Qualy, Richard J.,Gannett, Peter M.
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- Preparation of ABNO on Scale and Analysis by Quantitative Paramagnetic NMR
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A practical, safe, and scalable synthesis of the stable nitro-oxide radical catalyst ABNO was developed. This process is chromatography-free and avoids the Wolff-Kishner reduction. 1H NMR data for this paramagnetic compound were obtained that allowed an assessment of its chemical purity. Impact sensitivity test data for solid ABNO are also reported.
- Song, Zhiguo J.,Zhou, Guoyue,Cohen, Ryan,Tan, Lushi
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p. 1257 - 1261
(2018/09/06)
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