Zinc(II) complexes of xylyl bridged bis(1,4,7-triazacyclononane) derivatives

被引:20
作者
Fry, FH [1 ]
Fallon, GD [1 ]
Spiccia, L [1 ]
机构
[1] Monash Univ, Sch Chem, Clayton, Vic 3800, Australia
基金
澳大利亚研究理事会;
关键词
dinuclear complexes; zinc complexes; X-ray structures; NMR studies; bis(macrocyclic) ligands;
D O I
10.1016/S0020-1693(02)01390-7
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The xylyl bridged bis(tacn) ligands, T-2-o-X (1,2-bis(1,4,7-triazacyclonon-1-ylmethyl)benzene) and T-2-p-X (1,4-bis(1,4,7triazacyclonon-1-ylmethyl)benzene) have yielded one mononuclear, [Zn(T-2-o-X)](ClO4)(2) (1), and one dinuclear complex [Zn-2(T-2-p -X)(H2O)(4)(DMF)(2)][ZnCl4](2) (2). A single-crystal X-ray structure determination of 1 has established that T-2-o-X ligand sandwiches a single zinc(H) centre, which adopts a distorted octahedral geometry. A structural analysis of 2 confirmed the formation of a binuclear [Zn-2(T-2-p-X)(H2O)(4)(DMF)(2)](4+) complex in which each zinc centre binds to one of the macrocyclic compartments of the T2-P-X ligand and the remaining zinc coordination sites are occupied by water and DMF ligands. The coordination of DMF highlights the ability of carbonyl groups in amide molecules to bind to zinc(II), a feature of zinc enzymes that catalyse the hydrolysis of amide bonds in proteins (peptidases). A synthetic procedure has been developed which enables single pendant carboxymethyl groups to be attached to, T-2-o -X and T-2-m-X. These bis(tetradentate) ligands form dinuclear zinc(II) complexes [Zn-2(T-2-o-X AC(2))(H2O)(4)](ClO4)(2)-2H(2)O (3) and [Zn-2(T-2-m-X Ac-2)(H2O)(4)](ClO4)(2).2H(2)O (4), whose structure has been probed by spectroscopic methods. (C) 2002 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:57 / 66
页数:10
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