Copper(II) and zinc(II) dinuclear enzymes model compounds: The nature of the metal ion in the biological function

摘要

AbstractFirst series transition metals are used abundantly by nature to perform catalytic transformations of several substrates. Furthermore, the cooperative activity of two proximal metal ions is common and represents a highly efficient catalytic system in living organisms. In this work three dinuclear μ-phenolate bridged metal complexes were prepared with copper(II) and zinc(II), resulting in a ZnZn, CuCu and CuZn with the ligand 2-ethylaminodimethylamino phenol (saldman) as model compounds of superoxide dismutase (CuCu and CuZn) and metallo-β-lactamases (ZnZn). Metals are coordinated in a μ-phenolate bridged symmetric system. Cu(II) presents a more distorted structure, while zinc is very symmetric. For this reason, [CuCu(saldman)] shows higher water solubility and also higher lability of the bridge. The antioxidant and hydrolytic beta-lactamase-like activity of the complexes were evaluated. The lability of the bridge seems to be important for the antioxidant activity and is suggested to because of [CuCu(saldman)] presents a lower antioxidant capacity than [CuZn(saldman)], which showed to present a more stable bridge in solution. The hydrolytic activity of the bimetallic complexes was assayed using nitrocefin as substrate and showed [ZnZn(saldman)] as a better catalyst than the Cu(II) analog. The series demonstrates the importance of the nature of the metal center for the biological function and how the reactivity of the model complex can be modulated by coordination chemistry.Graphical abstractDisplay OmittedHighlights?Homo and heteronuclear Cu(II) and Zn(II) complexes with a μ-phenolate bridge structure in the solid state were obtained.?Zn(II) generates a stable dinuclear compound in solution.?Cu(II)Cu(II) generates a more labile bridge which is disrupted in solution resulting mononuclear species.?The following order of antioxidant and hydrolytic activity were found: [CuCu]<[CuZn]<[ZnZn].]]>