Up to four phenoxyl radicals coordinated to two metal ions in copper and zinc complexes?.

Neutral Cu(II) and Zn(II) complexes of the mono- and dinucleating Schiff base ligands (2,4-di-tert-butyl-6-({\{}2-[(3,5-di-tert-butyl-2-hydroxybenzylidene)amino]phenylimino{\}}methyl)phenol) and (2,4-di-tert-butyl-6-({\{}2,4,5-tri-[(3,5-di-tert-butyl-2-hydroxybenzylidene)amino]phenylimino{\}}methyl)phenol) resp. were synthesized and characterized. The monometallic complex can be oxidized into a mono and a dication, while oxidn. of the dimetallic one affords up to a tetracation. Whatever the ligand and metal are, oxidn. takes place at the phenolate moieties, which were oxidized into coordinated phenoxyl radicals, i.e. the oxidn. locus is not correlated to the ligand nuclearity. These results could be rationalized with previous ones by considering the hybridization of the coordinating nitrogens and the nature of the O-donor groups. [on SciFinder(R)]


Soumis le 12 avril 2018