Dinuclear metal(ii)-acetato complexes based on bicompartmental 4-chlorophenolate: syntheses, structures, magnetic properties, DNA interactions and phosphodiester hydrolysis.

A series of dinuclear metal(ii)-acetato complexes: [Ni2(μ-L(Cl)O)(μ2-OAc)2](PF6)·3H2O (1), [Ni2(μ-L(Cl)O)(μ2-OAc)2](ClO4)·CH3COCH3 (2), [Cu2(μ-L(Cl)O)(μ2-OAc)(ClO4)](ClO4) (3), [Cu2(μ-L(Cl)O)(OAc)2](PF6)·H2O (4), [Zn2(μ-L(Cl)O)(μ2-OAc)2](PF6) (5) and [Mn2(L(Cl)-O)(μ2-OAc)2](ClO4)·H2O (6), where L(Cl)O(-) = 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-chlorophenolate, were synthesized. The complexes were structurally characterized by spectroscopic techniques and single crystal X-ray crystallography. Six-coordinate geometries with doubly bridged acetato ligands were found in Ni(ii), Zn(ii) and Mn(ii) complexes 1, 2, 5 and 6, whereas with Cu(ii) complexes a five-coordinate species was obtained with 4, and mixed five- and six-coordinate geometries with a doubly bridged dimetal core were observed in 3.

Magnetic and structural properties of dinuclear singly bridged-phenoxido metal(II) complexes.

The reaction of a methanolic solution containing the bi-compartmental phenolic ligand 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-chlorophenol (L(Cl)-OH) with MCl2·nH2O in the presence of NH4PF6 or NaClO4 afforded the dinuclear bridged-phenoxido dichlorido-metal(ii) complexes [Co2(μ-L(Cl)O)(H2O)2Cl2][Co2(μ-L(Cl)O)(MeOH)2Cl2](PF6)2 (), [Ni2(μ-L(Cl)O)(MeOH)2Cl2]PF6 (), [Ni2(μ-L(Cl)O)(MeOH)(H2O)Cl2]ClO4·1.25H2O (), [Cu2(μ-L(Cl)O)Cl2]PF6·1/2MeOH () and [Zn2(μ-L(Cl)O)Cl2]PF6·MeOH (). The complexes were characterized by elemental microanalyses, conductivity measurements, IR and UV-Vis spectroscopy, mass spectrometry and single crystal X-ray crystallography.