This microreview describes the structures, properties and mechanisms of three selected bimetallic enzymes: Cu‐Zn superoxide dismutase (SOD), purple acid phosphatases (PAPs) and catechol oxidases (COs). The relevance of the unsymmetrical structures in the binucleating environment to the reaction mechanism and the respective roles of each metal center of these enzymes are discussed. Relevant model compounds are also considered. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
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