FeCl_3/磷酸三丁酯催化四氯化碳与氯乙烯的调聚反应:结构与活性  

FeCl_3/Tributyl Phosphate Complex as Catalyst in Telomerization of Tetrachloromethane with Chloroethylene: Structure and Activity

作　　者：曾纪珺[1] 韩升[1] 唐晓博[1] 张伟[1] 吕剑[1] 

机构地区：[1]西安近代化学研究所,陕西西安710065

出　　处：《分子催化》2015年第1期1-8,共8页Journal of Molecular Catalysis(China)

基　　金：陕西省科技统筹创新工程计划项目(2012KTCL01-01)

摘　　要：以四氯化碳与氯乙烯的调聚反应为目标反应,研究了Fe Cl3/磷酸三丁酯(TBP)配合物在反应体系中的结构,并关联了其结构与催化活性.采用摩尔电导、红外光谱和紫外吸收光谱对配合物的结构进行表征,结果表明Fe Cl3/TBP配合物在四氯化碳溶剂中为加合物Fe Cl3(TBP)n(n=1,2和3),配位数n由TBP与Fe Cl3的化学计量数决定.通过表观动力学实验研究了该配合物的催化反应活性,实验结果表明反应表观速率常数(kobs)随着TBP与Fe Cl3的摩尔比(r)的增大而增大,反应引发期(t0)随着r的增大而减小.假定反应遵循链式氧化还原机理,推导了kobs和t0的表达式,表达式和实验结果一致,均表明kobs只与配合物Fe Cl3(TBP)n的配位数和浓度有关.The Fe Cl3 complex of tributyl phosphate( TBP) ligand had been tested in telomerization of tetrachloromethane with chloroethylene promoted by Fe / Fe Cl3 redox catalyst. The structural of the Fe Cl3/ TBP complex was investigated by molar conductance analysis,IR spectra and UV-vis spectra. In the reaction system,The Fe Cl3/ TBP complex is Fe Cl3( TBP)nadduct,the coordination numbers of the adduct are 1,2 and 3,which are equal to the stoichiometrie of TBP to Fe Cl3. Kinetic results showed that the apparent rate constant kobsincreases gradually with the increase of the molar ratio of TBP and Fe Cl3( r),while the reaction induction period t0 is decreased gradually with the increase of r. Assuming that the telomerization reaction follows a chain redox-catalytic mechanism,the expressions of kobsand t0 are derived,the expressions are consistent with the experimental data,and the expression and experimental data all show that the kobsis related with the coordination number and concentration of Fe Cl3( TBP)ncomplexes.

关 键 词：调聚反应 四氯化碳 铁基催化剂 动力学 链式氧化还原机理 

分 类 号：O621.25[理学—有机化学]