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

Two copper(II) complexes [Cu(L1)Cl] (1) and [Cu(L2)Cl] (2) were synthesized from tridentate ligands HL1 and HL2 involving a (Nquinoline,Nazo,Ophenol) donor set. The copper(II) ion is tetracoordinate with a chloride ion occupying the 4th position of the coordination sphere. Both x-ray diffraction and EPR spectroscopy reveal that the copper(II) ion geometry is square planar in 1. In contrast, significant tetrahedral distortions are obsd. in 2, as a result of the steric clash between the hydrogen atoms of the Me substituent of the quinoline group and the chloride ion. Cyclic voltammetry curves of 1 and 2 in CH2Cl2 display a reversible oxidn. wave at E1/2 = 0.59 V and 0.56 V vs. ferrocenium/ferrocene, resp., which was assigned to the phenoxyl/phenolate redox couple. Compds. 1+ and 2+ were generated and characterized by UV/visible and EPR spectroscopy. Their reactivity with benzyl alc. was studied by kinetic measurements. [on SciFinder(R)]

Références

Titre
Copper(II)-Coordinated α-Azophenols: Effect of the Metal-Ion Geometry on Phenoxyl/Phenolate Oxidation Potential and Reactivity.
Type de publication
Article de revue
Année de publication
2014
Revue
Eur. J. Inorg. Chem.
Volume
2014
Pagination
4263–4267
ISSN
1434-1948
Soumis le 12 avril 2018