AQUEOUS ELECTROCHEMISTRY OF MONONUCLEAR AND BINUCLEAR COPPER(II) COMPLEXES WITH POLYAZA[N]PARACYCLOPHANE LIGANDS

被引:20
作者
DOMENECH, A [1 ]
FOLGADO, JV [1 ]
GARCIAESPANA, E [1 ]
LUIS, SV [1 ]
LLINARES, JM [1 ]
MIRAVET, JF [1 ]
RAMIREZ, JA [1 ]
机构
[1] UNIV JAUME 1,DEPT EXPTL SCI,ORGAN CHEM LAB,E-12080 CASTELLO DE PLANA,SPAIN
来源
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1995年 / 04期
关键词
D O I
10.1039/dt9950000541
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The aqueous electrochemistry of the Cu2+ complexes of the azaparacyclophanes 2,6,9,13-tetraaza[14]paracyclophane (L1), 2,5,8,11-tetraaza[12]paracyclophane (L2) and 2,5,8,11,14-pentaaza[15]paracyclophane (L3) has been studied. Copper(II) forms stable mononuclear [CuH,L](2+r)+ species with all three ligands (r = -1 to 1, L1 and L2; -1 to 2, L3) while L2 and L3 also form binuclear [Cu2H(r)L](4+r)+ species (r = -2, L2; 0 to -2, L3) in a pH-dependent stepwise manner. Frozen-solution ESR measurements show that all the complexes prefer a square-planar co-ordination. In neutral and basic media reduction at mercury and glassy carbon electrodes occurs in two quasi-reversible steps, indicating the formation of stable Cu+ species. Stabilization of the Cu+ complexes with respect to disproportionation in the order L3 > L1 > L2 has been found.
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页码:541 / 547
页数:7
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