Structural states of the binuclear copper cluster of Cancer magister methemocyanin

Abstract The binuclear cupric copper cluster of Cancer magister methemocyanin prepared from hemocyanin and hydrogen peroxide is diamagnetic (1). Upon treatment with azide, it is transformed into magnetic dipolar coupled (paramagnetic) Cu(II) pairs and then into magnetically isolated Cu(II) complexes. This progressive uncoupling of the binuclear cupric pairs in methemocyanin is interpreted in terms of a relaxation of superexchange through one or more bridging ligands.