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研究论文

二茂金属共轭大环配体配合物的结构及性质

尹业高;张恭启;黄永德   

  1. 荆州师范高等专科学校化学系;香港大学化学系
  • 发布日期:1999-01-15

Syntheses, crystal structure and properties of complexes of metallocene-conjugated macrocyclic ligand

Yin Yegao;Zhang Gongqi;Huang Yongde   

  • Published:1999-01-15

报道了配体N-(二茂铁基甲基)-1,4,7-氮杂-9-冠-3(L1)和N-(二茂钌基甲基)-1,4,7-氮杂-9-冠-3(L2)的Co(III)和Fe(III)配合物1-4的合成及电化学性质。配合物[Co(III)2(L1)2(AcO)2(OH)](ClO4)(I)2(1)的晶体结构显示这些配合物具有线型排列的四金属中心结构。电化学研究表明:在这些配合物中,客体金属离子通过分子片断的电子传递作用使二茂金属的金属中心的氧化电位发生正移动。同时,不同二茂金属的取代效应也使相同客体金属离子的氧化电位不同。在两个二茂金属之间由于被大环1,4,7-氮杂-9-冠-3(tacn)和客体金属离子M^3^+构成的配位部分所分隔没有相互作用,而由μ-AcO^-和μ-OH^-所桥联的两个客体金属离子之间却存在着相互耦合,以致在电化学循环过程中观察到了混合价电化学产物的存在。

关键词: 二茂铁P, 共轭(化学键), 大环化合物, 配位体, 络合物晶体结构, 电化学, 相互作用

Four complexes ([Co(III)2(L1)2(AcO)2(OH)](AcO)(I)2 . 4H2O 1, [Fe(III) 2(L1)2(AcO)2(OH)](ClO4)2(I) 2, [Co(III)2(L1)2(AcO)2(OH)](ClO4)3 . 4H2O 3, and [Fe(III)2(L1)2(AcO)2(OH)](AcO)(ClO4)2 . 4H2O 4) (where L1=N- ferrocenylmethyl-1, 4, 7-triazacyclononane and L2=N-ruthenocenylmethyl- 1, 4, 7-triazacyclononane). were synthesised and characterized. Crystal structure of 1 shows that the complexes have a linearly arranged four-core skeleton which can be depicted as Mc-B-M-B'-M-B-Mc (where Mc represents metallocenylCunit, B and B' represent bridging groups). Electrochemical investigation of these complexes confirms that introduction of the guest metal ions, M, onto the free ligand induces an anodic shift of the redox potential of metallocene and, at the same time, that coordination of ligand to the metal ions causes change in the electrochemical behavior of the guest ion. No interaction is observed between two metallocene components separated by TACN-M(III) fragment, but an interaction between two guest ions is emphasized by the capture of mix-valence species during the course of electrochemical investigation.

Key words: FERROCENE P, CONJUGATE, MACROCYCLIC COMPOUNDS, LIGANDS, CRYSTAL STRUCTURE OF COMPLEX, ELECTROCHEMISTRY, INTERACTIONS

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