钛锆钒异核双金属配合物[Cp_2V(μ-η~2:η~4-PhC_4Ph)MCp_2′](M=Ti,Zr;Cp′=C_5H_5,C_5H_4SiMe_3)的合成与表征  

Synthesis and Crystal Structure of Heterodimetallic Complexes[Cp_2V(μ-η~2∶η~4-PhC_4Ph)MCp_2′](M=Ti,Zr;Cp′=C_5H_5,C_5H_4SiMe_3)

作　　者：赵建社[1] 顾爱萍[1] 何水样[1] Robert Choukroun Lydie Valade Patrick Cassoux 

机构地区：[1]西北大学化学系,西安710069 [2]法国国家科研中心配位化学实验室,法国图卢兹31062

出　　处：《高等学校化学学报》2002年第10期1833-1836,共4页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号 :2 0 0 710 2 7);陕西省科委自然科学基金 (批准号:2 0 0 0 H0 4);陕西省教育厅专项基金 (批准号 :0 0 JK13 0 );1999年教育部留学回国人员基金资助

摘　　要：室温下 ,[Cp2 Ti(C≡ CPh) 2 ],[Cp2 Zr(C≡ CPh) 2 ]和 [(C5H4 Si Me3) 2 Zr(C≡ CPh) 2 ]分别与二茂钒作用 ,合成了 [Cp2 V(μ-η2∶ η4 -Ph C4 Ph) MCp2 ′](1 ,M=Ti,Cp′=C5H5;2 ,M=Zr,Cp′=C5H5;3 ,M=Zr,Cp′=C5H4 Si Me3) .用元素分析、质谱、核磁共振谱、磁矩、红外和拉曼光谱对配合物进行了表征 . 3个配合物具有相似的磁化率 ,配合物 3的晶体结构分析表明 Ph C4 Ph通过内部 2个碳原子键合到 Cp2 V上 ,内部 2个碳原子和外部 2个碳原子均与 Cp2 ′Zr键合 ,丁二烯骨架内部的The reaction of [Cp 2Ti(C≡CPh) 2], [Cp 2Zr(C≡CPh) 2], [(C 5H 4SiMe 3) 2Zr(C≡CPh) 2] and vanadocene in toluene was performed at room temperature and gave heterodimetallic complexes[Cp 2V(μ-η 2∶η 4-PhC 4Ph)·MCp 2′] (1, M=Ti, Cp′=C 5H 5; 2, M=Zr, Cp′=C 5H 5; 3, M=Zr, Cp′=C 5H 4SiMe 3), respectively. These compounds, which have been characterized by elemental analysis, mass spectrometry, 1H NMR, IR and Raman spectroscopy, exhibit similar magnetic susceptibilities. According to an X-ray diffraction analysis of compound 3, the Cp 2V and Cp 2′Zr metallocene moieties are bonded to a butadiene(or butadiyne) framework via the two internal carbon atoms for Cp 2V, and via both the two internal carbon atoms and the two external carbon atoms for Cp 2′Zr. The distances and angles observed around the internal carbon atoms of the butadiene framework indicate that both internal carbon atoms of butadiene skeleton are planar and tetracoordinated.

关 键 词：合成 表征 异核双金属配合物 结构解释 钛 锆 钒 X射线衍射 

分 类 号：O614.41[理学—无机化学] O614.511[理学—化学]