化学学报 ›› 2002, Vol. 60 ›› Issue (4): 687-691. 上一篇    下一篇

研究论文

新颖结构的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)

赵建社;顾爱萍;何水样;Choukroun Robert;Valade Lydie;Cassoux Patrick   

  1. 西北大学化学系,西安(710069);法国国家科研中心配位化学实验室.法国,图 卢兹(31077)
  • 发布日期:2002-04-15

Novel Heterometallic Complexes [Cp_2V(μ-η~2:η~4-butadiyne)MCp_2] (M = Ti, Zr)

Zhao Jianshe;Gu Aiping;He Shuiyang;Choukroun Robert;Valade Lydie;Cassoux Patrick   

  1. Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Department of Chemistry, Northwest University,Xi'an(710069);Laboratory of Coordination Chemistry, CNRS.France,Toulouse
  • Published:2002-04-15

室温下,[Cp_2Ti(C≡CPh)_2]和[Cp_2Zr(C≡CPh)_2]分别与二茂钒作用,首次 合成了[Cp_2V(μ-η~2:η~4-PhC_4Ph)MCp_2] 1 (M = Ti), 2 (M = Zr)。用元素 分析、质谱、磁矩、红外和拉曼光谱对配合物进行了表征,两个配合物具有相似的 磁化率,配合物2的晶体结构分析表明PhC_4Ph通过内部两个碳原子键合到Cp_2V上 ,内部两个碳原子和外部两个碳原子均与Cp_2Zr键合,丁二烯骨架内部的两个碳原 子都具有四配位的平面结构。用核磁跟踪技术初步探讨了合成反应机理。

关键词: 钛络合物, 锆络合物, 钒络合物, 元素分析, 红外分光光度法, 喇曼光谱法, 晶体结构, 丁二烯, 反应机理

The reaction of [Cp_2Ti(C≡CPh)_2], [Cp_2Zr(C≡CPh)_2]with vanadocene in toluene at room temperature gives heterodimetallic complexes [Cp_2V(μ-η~2:η~4-butadiyne)MCp_2] 1 (M = Ti), 2 (M = Zr), respectively. These compounds, which have been characterized by elemental analysis, mass spectrometry, IR and Raman spectroscopy, exhibit similar magnetic susceptibilities. According to an X-ray diffraction analysis of 2, the Cp_2V and Cp_2Zr metallocene moieties are bonded to 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_2Zr. 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.

Key words: TITANIUM COMPLEX, ZIRCONIUM COMPLEX, VANADIUM COMPLEX, ELEMENTAL ANALYSIS, IR, RAMAN SPECTROMETRY, CRYSTAL STRUCTURE, BUTADIENE, REACTION MECHANISM

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