Copper(II) complexes of bis(benzimidazol-2-yl)-2-oxopropane (bbmo), [Cu(bbmo)(py)2](ClO4)2, [Cu(bbmo)(γ-pic)2](ClO4)2(CH3CN), [Cu(bbmo)(2-acpy)](ClO4)2(H2O)0.5, and [Cu(bbmo)(nmim)2](ClO4)2, where py=pyridine, γ-pic=4-methylpyridine, 2-acpy=2-acetylpyridine, and nmim= 4-methylimidazole, have been synthesized, and characterized by elemental analyses, infrared, electronic absorption, and EPR spectroscopic measurements. These complexes are either five coordinated square pyramidal or six coordinated elongated octahedral structures, with a facially bonded bbmo. Both py and γ-pic nuclei are perpendicular to the main coordination plane. Based on Gaussian analyses of the component bonds of the visible electronic spectra for these copper(II) complexes, the sequences of the d orbitals have been assigned as dxy >> dz2 > dx2-y2 > dyz > dxz for the elongated Oh or square pyramidal complexes. In conclusion, the bbmo tridentate ligand binds to copper d orbitals as a π-donor. Both [Cu(bbmo)(py)2]2+ and [Cu(bbmo)(γ-pic)2]2+ exhibit excellent catalytic capabilities in some oxidation reactions. First, as tyrosinase, both 3,5-di-t-butylcatechol and 2,4-di-t-butylphenol are oxidized by O2 forming 3,5-di-t-butylquinone; secondly, the oxidation of lithium benzyloxide by O2 forms benzaldehyde; and thirdly, the oxidation of thioanisole by O2 results in the forming of methyl phenyl sulfoxide. It is likely that the catalytic species are either μ-η2:η2-peroxo dicopper(II) or bis(μ-oxo)dicopper(Ⅲ) complexes.
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