稳定的肼和推拉(对映)氨基自由基

Patai's Chemistry of Functional Groups Pub Date : 2017-09-15 DOI:10.1002/9780470682531.PAT0920

A. Balaban

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引用次数: 2

摘要

电子顺磁共振波谱是目前研究自由基的首选方法。推拉氨基表现出特殊的稳定性，这可以用Linnett的电子自旋双四重奏理论满意地解释。稳定的肼，如2,2-二苯基-1-苦基肼基和2,2-二苯基-1-氰肼基，实际上可以看作是推拉型氨基基。Linnett理论的一个结果是肼基中神经网络键的键序增加，这是由x射线晶体学和高分子内旋转势垒实验证实的。对于氮中心不在环上的胺基和肼基，本综述列出了迄今为止已知的各种电子给体和电子受体。关键词:氨基、肼基稳定自由基;氮中心持久性自由基;推挽式稳定;capto-dative稳定;merostabilization;电子顺磁共振谱

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Stable Hydrazyls and Push–Pull (Capto-Dative) Aminyl Free Radicals

Electron paramagnetic resonance spectroscopy is at present the preferred method for studying free radicals. Push–pull aminyls show exceptional stability, which is explained satisfactorily by Linnett's double-quartet theory in terms of electronic spin. Stable hydrazyls such as 2,2-diphenyl-1-picrylhydrazyl and 2,2-diphenyl-1-cyanohydrazyl can actually be viewed as push–pull aminyls. A consequence of Linnett's theory is the increased bond order for the NN bond in hydrazyls, which is confirmed experimentally by X-ray crystallography and the high intramolecular rotation barrier. For aminyls and hydrazyls whose nitrogen center is not part of a ring, this survey lists the variety of electron donors and electron acceptors known so far. Keywords: aminyl and hydrazyl stable free radicals; nitrogen-centered persistent free radicals; push–pull stabilization; capto-dative stabilization; merostabilization; electron paramagnetic resonance spectra

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Patai's Chemistry of Functional Groups

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