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本文用自旋捕捉技术、柱色谱与ESR波谱相结合的方法,研究了Ph_3M(M=N、P,As,Sb,Bi)光解过程的活泼自由基。从自旋捕捉剂亚硝基特丁烷 (t-BuNO)、苯亚甲基叔丁基氮氧化合物(PBN)或2,3,4,6-四甲基亚硝基苯(ND)与活泼自由基形成的自旋加合物的ESR波谱的超精细结构,确证这些化合物光解过程中有Ph·自由基存在。从而可推断它们的光解初级过程包括Ph_3M的均裂,即Ph_3M→Ph_2M·+Ph·。此外,因Ph—M键能的大小顺序为 Pb—P>Ph—As>Pb—Sb>Ph—Bi所以Ph_2M·(M=As,Sb,Bi)的分解比Ph_2P·容易,实验中只检查出Ph_2P·,则正是所预期的。
In this paper, the free radicals of Ph_3M (M = N, P, As, Sb, Bi) photolysis process were studied by means of spin catching, column chromatography and ESR spectroscopy. From the spin traps nitroso-butane (t-BuNO), benzylidene tert-butyl oxynitride (PBN) or 2,3,4,6-tetramethylnitrosobenzene (ND) The ultrafine structure of the ESR spectrum of the spin adducts formed by the living free radicals confirmed the presence of Ph · radicals during the photolysis of these compounds. It can be inferred that their primary photolysis processes include the cleavage of Ph_3M, that is, Ph_3M → Ph_2M · + Ph ·. In addition, Ph_2M · (M = As, Sb, Bi) decomposes more easily than Ph_2P · due to the order of Pb-P> Ph-As> Pb-Sb> It is exactly what Ph_2P · is expected to be.