水合希土硝酸盐与本并及单环己基－12－冠－4配合物的合成、性质及晶体结构  

SYNTHESES AND PROPERTYS OF RARE EARTH NITRATE COMPLEXES WITH BENZO-12-C-4 AND CYCLOHEXYL-12-C-4

作　　者：王瑞瑶[1] 李振祥[1] 金钟声[1] 倪嘉缵[1] 

机构地区：[1]中国科学院长春应用化学研究所

出　　处：《无机化学学报》1994年第2期172-177,共6页Chinese Journal of Inorganic Chemistry

摘　　要：在乙腈介质中合成了苯并－１２－冠－４（简称Ｂ－１２－Ｃ－４）和单环己基－１２－冠－４（简称Ｃｙ－１２－Ｃ－４）的六种希土配合物：ＲＥ（ＮＯ３）３·Ｂ－１２－Ｃ－４（ＲＥ＝Ｐｒ，Ｇｄ，Ｙｂ，Ｌｕ），ＲＥ（ＮＯ３）３·Ｃｙ－１２－Ｃ－４（ＲＥ＝Ｌａ，Ｌｕ）．研究了它们的ＩＲ及１ＨＮＭＲ性质，并测定了四种单晶的结构．用ＩＮＤＯ法计算了Ｌｕ（ＮＯ３）３·Ｂ－１２－Ｃ－４，Ｌｕ（ＮＯ３）３·Ｃｙ－１２－Ｃ－４的电子结构．结果表明．Ｂ－１２－Ｃ－４与希土的配合物稳定性按Ｐｒ，Ｇｄ，Ｙｂ，Ｌｕ顺序减弱，并且Ｃｙ－１２－Ｃ－４与希土的配位能力大于Ｂ－１２－Ｃ－４．发现冠醚分子通过自身不同程度的扭曲，改变冠醚环空穴的大小，实现与不同大小的希土离子的配位作用．By reaction of RE(NO3)3· nH2O with benzo-12-C-4 or cyclohexyl-12-C-4 (in molar ratio 1: 1) in acetonitrile, six anhydrous complexes, RE(NO3)3·benzo-12-C-4(RE = Pr, Gd,Yb, Lu) and RE(NO3)3·cyclohexyl-12-C-4(RE= La, Lu), were obtained. They were characterized by IR and 1H NMR. The crystal structures of RE(NO3)3·benzo-12-C-4(RE= Gd,Lu) and RE(NO3)3·cyclohexyl-12-C-4(RE = La, Lu) were determined by X-ray diffraction analysis. The electronic structures of Lu(NO3)3·L(L=benzo-12-C-4, cyclohexyl-12-C-4)were studied by INDO method. The results showed that the stability of rare earth complexes of benzo-12-C-4 decreased within Pr, Gd, Yb, Lu series, and complexes of cyclohexyl-12-C-4 were more stable than complexes of benzo-12-C-4. It was found that the ether rings of the ligands occured some deformation when complexed with different rare earth ions.

关 键 词：合成 结构 冠醚配合物 稀土硝酸盐 

分 类 号：O613.61[理学—无机化学]