Pd(OAc)_2与有机双膦在氯代烷中的反应机理(Ⅱ)研究  

THE REACTION MECHANISM OF Pd(OAc)_2 WITH PHOSPHINE IN ALKANE CHLORIDE(Ⅱ)

作　　者：韦凤萍[1] 杨帆[1] 黄永仁[1] 冯良波[2] 汪汉卿[2] 

机构地区：[1]华东师范大学量子光学与波谱学国家重点实验室,化学系上海200062 [2]中国科学院兰州化学物理研究所,兰州730000

出　　处：《波谱学杂志》2000年第4期297-303,共7页Chinese Journal of Magnetic Resonance

基　　金：上海市高等学校青年科学基金!( 98QN1 2 )

摘　　要：在前文[1 ,2 ] 基础上 ,扩展了有机双膦系列 .应用电子自旋捕获技术 (EPR ST)研究了Pd(OAc) 2 与系列有机双膦dppm(二 (二苯基膦甲烷 ) )、dppe(二 (二苯基膦乙烷 ) )及dppp(二(二苯基膦丙烷 ) )在氯代烷中反应的反应机理 ,所用捕获剂为PBN ,得到EPR实验谱并进行了模拟 .提出了反应机理并进行了讨论 .并对影响反应的一些因素进行了探讨 .Pd(OAc) 2 在此反应中既是反应物又是引发剂 ,在反应中起分子诱导作用 .当Pd(OAc) 2 与非自由基物种有机双膦配体及氯代烷共存时 ,引发了自由基反应 .The new reaction mechanism of Pd(OAc)\-2 with dppm, dppe and dppp in different chlorinated alkane solvents was studied by EPR ST method. The used capturer was PBN. The obtained experimental spectra were simulated. The reaction mechanism is given and discussed. In these processes, the joining of Pd(OAc)\-2 made the activation energy lower. Some influence factors on the reaction are tentatively discussed. It was shown that the solvents were both reactant and solvents and Pd(OAc)\-2 was both reactant and initiator. It affected the reaction by its molecular induced action. When compounds that were not the source of free radical were put together, the free radical reaction happened. \;

关 键 词：PD(OAC)2 EPR-ST 自由基 氯代烷 膦 

分 类 号：O614.823[理学—无机化学]