稀土配合物催化碳二亚胺与膦氢化合物的反应  

Reaction of Phosphines with Carbodiimides Catalyzed by Rare Earth Complexes

作　　者：杨双兰 李荣龙[1,3] 冉巍巍 李峥嵘 王连军 易兵[1] 

机构地区：[1]湖南工程学院化学化工学院,湖南湘潭411104 [2]北京大学化学与分子工程学院,北京100871 [3]中山约克夏染料(助剂)有限公司,广东中山528445 [4]五邑大学纺织服装学院,广东江门529020

出　　处：《中国稀土学报》2018年第1期93-100,共8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(2014FJ2013)资助

摘　　要：以4种不同的稀土配合物RE(Ln)(Ln=La,Sc,Y和Lu)为催化剂催化膦氢化物与碳二亚胺的类似成胍反应,详细探讨了催化剂种类及用量、溶剂、温度及反应时间对各种反应底物的影响,合成了系列不同类型的膦杂胍化合物。研究表明:无催化剂,该类型的成胍反应不能发生,不同类型的稀土配合物,其催化活性不同,以离子半径较大的镧稀土配合物的催化活性最大;反应温度和反应时间取决于溶剂的溶解性以及底物的类型;碳二亚胺的取代基位阻及膦氢化物的酸性是影响反应底物能否顺利进行该类反应的关键因素;通过原位核磁分析该类型的反应经历了稀土配合物与膦化合物酸碱反应、碳二亚胺的插入反应、稀土配合物的解离以及质子的迁移过程形成催化循环及生成产物。The phosphaguanylation reaction of phosphines with carbodiimides was catalyzed by four different rare earth complexes RE （Ln） （ Ln = La, Sc, Y and Lu） , a series of phosphaguanylations with various structures were smoothly synthesized under different reaction conditions and different substrates including catalysts, solvents, tem- peratures and time. Detailed research showed that the phosphaguanylation reactions of phosphines with carbodiimides could not happened without suitable catalysts. The catalytic activity of these rare earth complexes relied mainly on the ionic radius of rare earth metals, thus complex La was found to display the highest activity among the rare earth metals owing to its largest ionic radius, however, the corresponding lutetium complex showed evidently lower activity. The reaction temperature and reaction time depended strongly on the solubility of solvents and the type of the substrates. The steric hindrance at the nitrogen atom of carbodiimides and the acidity of phosphines played an important role in this process. A tentative mechanism for the formation phosphaguanylation reactions involving the acid-base reaction between a phosphine and RE （ Ln）, the insertion reaction of carbodiimide, disassociation of rare- earth complex from intermediate and the intramolecular proton shift was proposed by in situ NMR monitoring, sim- ultaneously, the phosphaguanidine products and the regenerated rare-earth complex catalyst to finish the catalytic could be perfectly achieved.

关 键 词：稀土配合物 碳二亚胺 膦氢化合物 催化 原位核磁 

分 类 号：TQ613.1[化学工程—精细化工]