Formation of out of plane oxime metallacycles in [Cu2] and [Cu4] complexes

Abstract: The reaction of Cu(ClO4)2·6H2O with dimethylglyoxime (H2dmg) in a 1:1 mole ratio in aqueous methanol at room temperature affords the dinuclear complex [Cu2(μ-Hdmg)4] (1). Reaction of 1 with [Cu(bpy)(H2O)2](ClO4)2 (bpy=2,2′-bipyridine) in a 1:1 mole ratio in aqueous methanol at room temperature yields the tetranuclear complex [Cu4(μ-Hdmg)2(μ-dmg)2(bpy)2(H2O)2](ClO4)2 (2). The direct reaction of Cu(ClO4)2·6H2O with H2dmg and bpy in a 2:2:1 mole ratio in aqueous methanol at room temperature also yields 2 quantitatively. The complexes 1 and 2 were structurally characterized by X-ray crystallography. Unlike the binding in Ni/Co-dmg, two different types of N−O bridging modes during the oxime based metallacycle formation and stacking of square planar units have been identified in these complexes. The neutral dinuclear complex 1 has CuN4O coordination spheres and complex 2 consists of a dicationic [Cu4(μ-Hdmg)2(μ-dmg)2(bpy)2(H2O)2]2+ unit and two uncoordinated ClO4 − anions having CuN4O and CuN2O3 coordination spheres. The two copper(II) ions are at a distance of 3.846(8)Å in 1 for the trans out of plane link and at 3.419(10) and 3.684(10)Å in 2 for the trans out of plane and cis in plane arrangements, respectively. The average Cu–Noxime distances are 1.953 and 1.935Å, respectively. The average basal and apical Cu−Ooxime distances are 1.945, 2.295 and 2.429Å. The UV–Vis spectra of 2 is similar to the spectrum of the reaction mixture of 1 and [Cu(bpy)(H2O)2]2+. Variable temperature magnetic properties measurement shows that the interaction between the paramagnetic copper centers in complex 1 is antiferromagnetic in nature. The EPR spectra of frozen solution of the complexes at 77K consist of axially symmetric fine-structure transitions (ΔM S =1) and half-field signals (ΔM S =2) at ca. 1600G, suggesting the presence of appreciable Cu–Cu interactions. [Copyright &y& Elsevier]