Copper(II) catalyses the reduction of perchlorate by both formaldehyde and by dihydrogen in aqueous solutions

During an effort to synthesize the trans-III-copper(II) complex with 1,4,8,11-tetramethyl-pyro-phosphonate-1,4,8,11-tetra-aza-cyclo-tetradecane, using only perchlorate salts, it was noted that the perchlorate is reduced to chloride. Analysis of the reactions leading to this surprising result points out that Cu(H2O)42+ catalyzes the reduction of perchlorate by H2 and by CH2O. These reactions are slow at room temperature and ambient pressures. A plausible mechanism, supported by DFT calculations, is proposed pointing out that the role of CuH+ under mild conditions cannot be ignored.