【摘要】 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Ph₃M（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Ph₃M的均裂,即Ph₃M→Ph₂M·+Ph·。此外,因Ph—M键能的大小顺序为 Pb—P>Ph—As>Pb—Sb>Ph—Bi所以Ph₂M·（M=As,Sb,Bi）的分解比Ph₂P·容易,实验中只检查出Ph₂P·,则正是所预期的。更多还原

【Abstract】 Active intermediates in the photolysis processes of compounds Ph₃M （M=N, P, As, Sb, Bi） have been studied with the combination of spin trapping technique, column chromatography and ESR spectrascopy. From the hyperfine structures of the ESR spectra of the spin adducts formed between active intermediates and spin trapping reagents such as phenyl tert-butyl nitrone （PBN）, nitrosobutane（t-BuNO） or nitrosodurene （ND）, the free radical Ph. has been identified in the photlysis of Ph₃M （M= P, As, Sb, Bi） and Ph₂P. has been detected for the case of Ph₃P. It could be concluded that the photochemical initial step of these compounds include the homolysis of Ph₃M, viz Ph₃M—→Ph₂M. +Ph.. As the average bond energies of Ph—M decrease in the order Ph—P>Ph—As>Ph—Sb>Ph—Bi Ph₂M. （M=As, Sb, Bi） decompose much easy than that of Ph₂P., So they could not be observed in our experiment.更多还原