1. Copper(II)-Coordinated α-Azophenols: Effect of the Metal-Ion Geometry on Phenoxyl/Phenolate Oxidation Potential and Reactivity.
- Author
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Kochem, Amélie, Carrillo, Alexandre, Philouze, Christian, van Gastel, Maurice, du Moulinet d'Hardemare, Amaury, and Thomas, Fabrice
- Subjects
METAL ions ,OXIDATION ,PHENOXIDES ,BENZYL alcohol synthesis ,METALLOENZYMES ,CHEMICAL reactions - Abstract
Two copper(II) complexes were synthesized from tridentate ligands involving a (N
quinoline ,Nazo ,Ophenol ) 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 CH2 Cl2 display a reversible oxidation wave at E1/2 = 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. [ABSTRACT FROM AUTHOR]- Published
- 2014
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