二茂锆羧酸配合物的合成——二茂锆氢化物与α,β—不饱和酸或钠盐反应的研究

SYNTHESIS OF ZIRCONOCENE CARBOXYLATE COMPLEXES——STUDY ON THE REACTIONS OF ZIRCONOCENE HYDRIDES WITH α,β-UNSATURATED ACIDS AND THEIR SALTS

本文研究了Cp_2ZrH_2与丙烯酸和Cp_2Zr(H)Cl与丙烯酸钠、巴豆酸钠的反应。产物由IR 1~H和^(13)CNMR、ESR谱、气相色谱以及化学方法分析鉴定。产物水解得到与底物相应的饱和酸.用~1H NMR方法考察了Cp_2ZrH_2与丙烯酸的反应过程,用IR方法考察了Cp_2Zr(H)Cl与丙烯酸钠的反应过程。实验结果表明,上面两种反应首先消除H_2或NaCl,形成锆氧健,然后碳碳双键还原生成二茂锆羧酸盐配合物,其中羧酸根离子与二茂锆桥式双齿配位。

The reactions of Cp2ZrH2with acrylic acid and Cp2Zr(H)Cl with sodium acrylate or crotonate have been investigated in our laboratory. The products were characterized by IR, 1H and 13C NMR, ESR spectra,GC and chemical methods. When the products were hydrolyzed their corresponding saturated acids were obtained. The process of Cp2ZrH 2 reacting with acrylic acid was examined by H NMR and Cp2Zr(H)Cl reacting with sodium acrylate by IR.The results showed that the reactions of Cp2ZrH2 with acrylic acid or Cp2Zr(H)Cl with sodium acrylate and crotonate eliminate H2or NaCl first, to form zirconium-oxygen bond, and then carbon-carbon double bond is reduced to yield products 1,2,3, respectively, in which carboxylic anions coordinated to the zirconocene as bridging bidentates.