(C_5H_9C_5H_4)_3NdBrLi(THF)_3和(C_5H_9C_5H_4)_3SmTHF的合成与结构

无水三氯化钕与环戊烷基环戊二烯钠、溴化锂(1:2:1摩尔比)反应,除去不溶物和溶剂后,产物在己烷/四氢呋喃溶剂中冷冻得到兰紫色晶体(C5H9C5H4)3NdBrLi(THF)3(配合物1)。其中心金属Nd3+的配位数为10,以η5与3个环戊二烯基相连,并通过单溴原子桥连锂原子,形成双核结构。该晶体属三斜晶系,P`1空间群。晶体学参数为a=12.048(2)、b=13.498(3)、c=13.831(3);α=104.16(3)、β=104.07(3)、γ=95.96(3); V=2083.3(7)3、Z=2、Dc=1.35Mg/m3、Mr=847.01gmol-1、F(000)=874。无水三氯化钐与环戊烷基环戊二烯钠(1:3)反应,产物在-30oC下的己烷溶剂中结晶得桔红色晶体(C5H9C5H4)3SmTHF(配合物2)。该晶体属正交晶系,Fdd2空间群。晶胞参数a=28.175(5) 、b=46.24(2)、c=9.167(4);V=11943(8)3、Z=16、Dc=1.38Mg/m3、 Mr=622.11 g·mol-1、F(000)=5136。10配位的金属Sm3+与3个环戊二烯基以η5相连,并结合一个四氢呋喃溶剂分子。

Synthesis and Characterization of Tris(cyclopentylcyclopentadienyl)lanthanide Complexes (C5H9C5H4)3NdBrLi(THF)3 and (C5H9C5H4)3SmTHF

C5H9C5H4)3NdBrLi(THF)4(1)(C5H9=cyclopentyl) was obtained from the reaction of NdCl3 withC5H9C5H4Na and LiBr (Nd:Na:Li=1:2:1 molar ratio) in THF. X-ray crystallography showed that theten-coordinated neodymium atom is bonded to three cyclopentylcyclopentadienyl(h5) rings and a singlebromine atom bridging a lithium which is bonded to three THF molecules. Complex 1 is triclinic, P space group with unit dimensions of a=12.048(2), b=13.498(3), c=13.831(3), α=104.16(3),β=104.07(3), γ=95.96(3), V=2083.3(7)3, Z=2, Dc=1.35Mg/m3 and F(000)=874. (C5H9C5H4)3SmTHF (2) was synthesized by reaction of anhydrous SmCl3 with C5H9C5H4Na at a molar ratio of 1:3. The structure was determined by X-ray crystallography. The ten-coordinated samarium atom is bonded to three cyclopentylcyclopentadienylrings and one oxygen of THF molecule to form a pseudo-tetrahedron. Complex 2 is orthorhombic, Fdd2 space group with unit cell dimensions of a =28.175(5), b =46.24(2) ?, c =9.167(4) ? V=11943(8)3, Z=16, Dc=1.38Mg/m3 and F(000)=5136.