稀土金属杂环戊二烯化合物的合成及其催化活性研究  

Synthesis and Catalytic Activity of Rare Earth Heterocyclopentadiene Compounds

作　　者：柳高 王连军[1] 李峥嵘[2,3] 王岩 陈建芳 Liu Gao;Wang Lianjun;Li Zhengrong;Wang Yan;Chen Jianfang(Key Laboratory of Environmental Catalysis and Waste Regeneration,College of Materials and Chemical Engineering,Hunan Institute of Engineering,Xiangtan 411104,China;College of Textiles and Clothing,Wuyi University,Jiangmen 529020,China;Zhongshan Yorkshire Dyes(Agent)Co.,Ltd.,Zhongshan 528445,China)

机构地区：[1]湖南工程学院材料与化工学院,环境催化与废弃物再生化重点实验室,湖南湘潭411104 [2]五邑大学纺织服装学院,广东江门529020 [3]中山约克夏染料(助剂)有限公司,广东中山528445

出　　处：《中国稀土学报》2019年第5期552-559,I0002,共9页Journal of the Chinese Society of Rare Earths

基　　金：湖南省高校创新平台开放基金项目(15K030);湖南省科技计划重点项目(2014FJ013)资助

摘　　要：以Cp*Li,稀土LCI3及二锂试剂a或b为原料,以THF为溶剂,合成了一系列单茂稀土金属杂环戊二烯,并对其结构和单晶分别用1H NMR,13C NMR核磁谱,FT-IR红外光谱,气相色谱-质谱仪及X射线单晶衍射仪进行了表征,其对胺(肼)与碳二亚胺反应的催化性能和机制进行了深人研究。结果表明:单茂钪杂环戊二烯的中心稀土原子Sc为六配位,一个五甲基环戊二烯阴离子以?5的配位模式与其相连,Sc原子还与两个二烯骨架的a-C以共价键的形式相连,形成Sc杂环戊二烯骨架。在Sc杂环戊二烯的结构单元中,Sc与其他4个C原子并不在同一个平面内,而是呈现出信封形的结构。单茂稀土杂环戊二烯能催化胺与碳二亚胺直接成脈,且催化性能与稀土离子的半径有关,在最佳条件下产物产率最高达到99%以上;单茂稀土杂环戊二烯也能催化肼与碳二亚胺反应,其催化机制主要与单茂稀土杂环戊二烯配位锂离子与肼的质子交换有关,其催化性能相近,与稀土离子无关,不同的肼,其产物不同,底物为1,2-二芳基肼与1,2-二环己基碳二亚胺.反应产物分别为脈h和反式偶氮苯I2,底物为1-甲基-1-苯基肼(或者1,1-二苯基肼)与1,2-二环己基碳二亚胺,反应产物为氨基肌类的化合物I3。A series of rare earth metallocene heterocyclic pentadienes were synthesized from Cp*Li,rare earth LC13 and lithium dioxide reagent a or b in THF.Their structures and single crystals were characterized by 1H NMR,13C NMR,FT-IR,GC-MS and X-ray single crystal diffraction,respectively.The properties and mechanism of catalytic reaction of amines or hydrazines with carbodiimides were studied in depth.The results showed that the central rare earth atom Sc of scandocene heterocyclic pentadiene is 6-coordinated,and a pentamethylcyclopentadiene anion is linked to it in the coordination mode of 7]5.The Sc atom was also linked to the C in the form of covalent bond,which formed backbone of Sc heterocyclic pentadiene.In the structural un让of SC heterocyclic pentadiene,Sc atom was not in the same plane as the other four C atoms,but presented an envelope-like structure.Mono cyclopentadiene(Cp)supported rare earth metallacyclopentadienes could catalyze the direct synthesis of guanidines from amines and carbodiimides,and the catalytic performance was related to the radius of rare earth ions.Under the optimum conditions,the yield of the product was up to 99%.Mono cyclopentadiene(Cp)supported rare earth metallacyclopentadienes could also catalyze the reaction of hydrazines with carbodiimides.Its catalytic mechanism was mainly related to the proton exchange between lithium ion and hydrazine.Its catalytic performance was similar,independent of rare earth ions,and different hydrazines had different products.If the substrates were 1,2-diaryl hy-drazines and 1,2-dicyclohexyl carbodiimides,products were guanidine I1and trans-azobenzene I2;If substrates were 1-methyl-1-phenylhydrazine(or 1,1-diphenylhydrazine)and 1,2-dicyclohexylcarbodiimides,the products were aminoguanidine compounds I3.

关 键 词：单茂稀土金属杂环戊二烯 单晶 催化活性 反应机制 

分 类 号：TQ252.1[化学工程—有机化工]