Formation constants and oxidation of bis(1,10-phenanthroline)copper(I) perchlorate and bis(2,2'-bipyridine)copper(I) perchlorate by molecular oxygen in formamide

A study was made of the slow oxidation with molecular oxygen in formamide of the cuprous complexes Cu(1,10-phenanthroline)(2)(+) and Cu(2,2'-bipyridine)(2)(+) and of Cu(MeCN)(4)ClO4 with and without complexing agents. The two formation constants were calculated from the kinetic data. Both complexes reacted with a rate constant of 0.001 with respect to the value obtained in solvent water. A catalytic effect of the water molecules is proposed to explain this difference. The cupric complexes formed were isolated and identified as [CuL(2) formate]ClO4 and [CuL(2) cyanate]ClO4.