Copper(II)-Coordinated α-Azophenols: Effect of the Metal-Ion Geometry on Phenoxyl/Phenolate Oxidation Potential and Reactivity

被引：11

作者：

Kochem, Amelie ^{[1
,2
]}

Carrillo, Alexandre ^{[2
]}

Philouze, Christian ^{[2
]}

van Gastel, Maurice ^{[1
]}

d'Hardemare, Amaury du Moulinet ^{[2
]}

Thomas, Fabrice ^{[2
]}

机构：

[1] Univ Grenoble Alpes, Dept Chim Mol, UMR CNRS 5250, F-38041 Grenoble 9, France

[2] Max Planck Inst Chem Energy Convers, D-45470 Mulheim, Germany

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2014年 / 26期

关键词：

Metalloenzymes; Oxidation; Copper; Ligand design; Tridentate ligands; Radicals; GALACTOSE-OXIDASE; COPPER(II) COMPLEXES; CU-II; MODELS; GOASE(SEMI); CATALYSIS;

D O I：

10.1002/ejic.201402312

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Two copper(II) complexes were synthesized from tridentate ligands involving a (N-quinoline, N-azo, O-phenol) donor set. The copper(II) ion is tetracoordinate with a chloride ion occupying the fourth position of the coordination sphere. Both X-ray diffraction and electron paramagnetic resonance (EPR) spectroscopy reveal that the copper(II) ion geometry is square planar in 1. In contrast, significant tetrahedral distortions are observed in 2, as a result of the steric clash between the hydrogen atoms of the methyl substituent of the quinoline group and the chloride ion. Cyclic voltammetry curves of 1 and 2 in CH2Cl2 display a reversible oxidation wave at E-1/2 = 0.59 V and 0.56 V versus ferrocenium/ferrocene, respectively, which was assigned to the phenoxyl/phenolate redox couple. Compounds 1(+) and 2(+) were generated and characterized by UV/Vis and EPR spectroscopy. Their reactivity with benzyl alcohol was investigated by kinetic measurements.

引用

页码：4263 / 4267

页数：5

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