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首页> 外文期刊>Bulletin of the Chemical Society of Japan >Synthesis and Redox Properties of Crowded Triarylphosphines Carrying a Nitroxide Radical and Related Compounds
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Synthesis and Redox Properties of Crowded Triarylphosphines Carrying a Nitroxide Radical and Related Compounds

机译：携带氮氧化物自由基的拥挤三芳基膦的合成和氧化还原性能

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摘要

Crowded triarylphosphines carrying a nitroxide radical were synthesized to investigate intramolecular interaction between the crowded triarylphosphine redox centers and a neutral radical. A crowded triarylphosphine carrying a bro-moaryl group was developed as a key synthetic intermediate. Lithiation of the (bromoaryl)phosphine, followed by re-action with 2-methyl-2-nitrosopropane, afforded a crowded triarylphosphine carrying a nitroxide after aerobic oxidation. Similar procedure using isoamyl nitrite (isoamyl = 3-methylbutyl) gave nitroxide and azobenzene derivatives with two crowded triarylphosphine moieties. The azobenzene derivative was alternatively prepared by photolysis of the corre-sponding (azidoaryl)phosphine. EPR spectra of the nitroxide radicals showed hyperfine couplings with ~(31)P nuclei, which were larger than previously reported phosphinoaryl nitroxide radicals. Cyclic voltammograms of the newly synthesized triarylphosphines showed reversible redox waves corresponding to the phosphorus redox centers. The two triarylphos-phine moieties connected by a nitroxide linkage showed a reversible two-step oxidation reflecting considerable interac-tion between the phosphorus redox sites across the nitroxide linkage. Oxidation of the crowded triarylphosphines carry-ing a nitroxide and photolysis of the chemically oxidized (azidoaryl)phosphine was studied by EPR spectroscopy.
机译：合成携带硝基氧化物的拥挤三芳基膦，以研究拥挤的三芳基膦氧化还原中心与中性自由基之间的分子内相互作用。携带博罗-Moaryl组的拥挤三芳基膦作为关键合成中间体。 （溴芳基）膦的锂化，然后用2-甲基-2-亚硝基丙烷重新作用，得到了一种拥挤的三芳基膦，在有氧氧化后携带硝基氧化物。使用异戊酯（异戊酰= 3-甲基丁基）的类似程序使硝基氧化物和三唑衍生物具有两个拥挤的三芳基膦部分。偶氮苯衍生物可替代地通过光解（氮杂芳基）膦光学来制备。硝基氧化物基团的EPR光谱显示出〜（31）P核的高血清偶联，其大于先前报道的磷芳基氧化物基团。新合成的三芳基膦的循环伏安图显示出与磷氧化还原中心相对应的可逆氧化还原波。通过硝基氧化物连杆连接的两个三芳基氏杂肽部分显示出可逆的两步氧化，反映了在氮氧化物键的磷氧化还原位点之间相当大的间隙。通过EPR光谱研究了含有氮氧化物的拥挤三芳基膦的拥挤三芳基膦和化学氧化（壬芳基）膦的光解。

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