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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

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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