EQUILIBRIUM AND STRUCTURAL STUDIES ON METAL-COMPLEXES OF OXIME LIGANDS - POLYNUCLEAR COMPLEX-FORMATION OF COPPER(II) WITH 3-AMINOPROPANAMIDOXIME AND ITS N-ALKYL DERIVATIVES

被引:12
作者
ORAMA, M
SAARINEN, H
KORVENRANTA, J
机构
来源
ACTA CHEMICA SCANDINAVICA | 1994年 / 48卷 / 02期
关键词
D O I
10.3891/acta.chem.scand.48-0127
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
The complex formation equilibria of copper(II) with 3-aminopropanamidoxime (HL = 1), 3-(methylamino)propanamidoxime (HL=2) and 3-(diethylamino)-propanamidoxine (HL = 3) were studied in aqueous 0.1 M NaCl at 25-degrees-C by a potentiometric method. Experimental data were analyzed with respect to the possible complexes and their stability constants, using the least-squares computer program SUPERQUAD. With all three ligands the best model was that including the mononuclear complexes Cu(HL)2+ and Cu(H2L)3+ and the pentanuclear species H-7Cu5(HL)43+ and H-8Cu5(HL)42+. In addition, a mononuclear bis complex Cu(HL)22+ was found for ligands 1 and 2 and a tetranuclear species H-6Cu4(HL)42+ for ligand 2. The crystal structure was determined by X-ray diffraction methods for the solid complex H-8Cu5(HL)4Br2.2H2O (HL = 2) isolated from the equilibrium solution. The compound crystallizes in the monoclinic space group P2(1)/c with the following cell parameters: a = 10.880(5), b = 5.930(3), c = 23.836(11) angstrom, beta = 100.06(4)degrees, and Z = 2. The structure consists of nearly planar divalent [Cu5(L-H)4]2+ complex moieties, bromide ions, and water of hydration. From a comparison of the compositions of the polynuclear complex in the aqueous and solid phases it was concluded that deprotonation of the aqueous complexes starts from the coordinated oxime and amide groups and that the formulas H-8Cu5(HL)42+ and H-6Cu4(HL)42+ should be written as [Cu5(L-H)4]2+ and [Cu4(L-H)2L2]2+, respectively.
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页码:127 / 133
页数:7
相关论文
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