We synthesized two dinuclear copper complexes, which have ionizable N imidazole and N pyrazole protons in the ligand, respectively, and determined the BDFE of the hypothetical H atom transfer reactions Cu-II(LH-1) + H-center dot <-> Cu-I(L) in MeOH/H2O (BDFE: bond dissociation Gibbs (free) energy). The ligands have two adjacent N,N',O-binding pockets, which differ in one N-heterocycle: L-a has an imidazole unit and L-c, a pyrazole unit. The copper(II) complexes of L-a and L-c have been characterized, and the substitution pattern has only little influence on the structural properties. The BDFEs of the hypothetical PCET reactions have been determined by means of the species distribution and the redox potentials of the involved species in MeOH/H2O (80/20 by weight). The pyrazole copper complex 3 exhibits a lower BDFE than the isoelectronic imidazole copper complex 1 (1, 292(3) kJ mol(-1); 3, 279(1) kJ mol(-1)). The difference is mainly caused by the higher acidity of the N pyrazole proton of 3 compared to the N imidazole proton of 1. The redox potentials of 1 and 3 are very similar.