（η^5—C5H5）3Ln·OC4H8（Ln=Ce,Er）的合成及晶体结构  

Syntheses and Crystal Structure of (η~5-C_5H_5)_3Ln·OC_4H_8(Ln = Ce, Er)

作　　者：陈文启[1] 林观阳[1] 夏巨松[1] 卫革成 张引[1] 金钟声[1] 

机构地区：[1]中国科学院长春应用化学研究所,长春130022

出　　处：《化学学报》1994年第3期261-267,共7页Acta Chimica Sinica

摘　　要：用无水硝酸铈铵［（ＮＨ４）２Ｃｅ（ＮＯ３）６］与环戊二烯钠（Ｃ５Ｈ５Ｎａ）在四氢呋喃中接１：６摩尔比反应，得到（η＾５－Ｃ５等５）３Ｃｅ·ＯＣ４Ｈ８；用ＥｒＣｌ３·ｎＴＨＦ与环辛二烯钾（Ｃ８Ｈ１１Ｋ）按等摩尔比于－７８℃反应，升至室温，再按１：２摩尔比加入Ｃ５Ｈ５Ｎａ，得到了（η＾５－Ｃ５Ｈ５）３Ｅｒ·ＯＣ４Ｈ８。两配合物晶体结构测定结果表明都属单斜晶系Ｐ２１／ｎ空间群。Tricyclopentadienyl cerium tetrahydrofuranate (THF) was prepared by the reaction of (NH4)2Ce(NO3)6 with sodium cyclopentadienide(C5H5Na)in THF at molar ratio of 1:6 to give a brown crystal of (η5-C5H5)3Ce·OC4H8; tricyclopentadienyl erbium tetrahydrofuranate complex was synthesized by the reaction of ErCl3·nTHF with potassium cyclooctadienide (C8H11K) at molar ratio of 1:1 at - 78℃, and tnen C5H5Na in THF (at molar ratio of ErCl3·nTHF to C5H5Na 1:2)was added to the above solution at room temperature to give the pink crystal of (η5-C5H5)3Er·OC4H8. The crystal structure determination of both complexes showed that both crystals belong to monoclinic space group P21/n. The Oe complex structure is different from those of (η5-C5H5)8Ln·OC4H8(Ln = La, Pr, Nd, Gd, Dy, Y, Lu). They are not isostructural, but the Er complex is isostructural with them. The distance Oe-O, av. Ce-C(η5) and Ce-Cent (Centroid of cyclopentadienyls) are not consistent with the lanthanide contraction regularity, but those of Er-O, av. Er-C(η5) and Er-Cent are consistent with it.It means that there are two discontinuity points at Oe and Dy but no 'gadolinium break phenomenon' is observed in the isostructural series of (η5-C5H5)3Ln·OC4H8 because the bond lengths of Ln-O and Ln-C(η5) and the Ln-centroid distance of the elements (Y, Er, Lu) are not greater than those of Gd.

关 键 词：环戊二烯 钆断 晶体 稀土络合物 

分 类 号：O614.33[理学—无机化学]