Novel Copper(II) Complexes with BIAN Ligands: Synthesis, Structure and Catalytic Properties of the Oxidation of Isopropylbenzene

Two new isomeric complexes [CuBr2(R-bian)] (R = 4-Me-Ph (1), 2-Me-Ph (2)) were obtained by reacting copper(II) bromide with 1,2-bis[(2-methylphenyl)imino]acenaphthene ligands and characterized. The crystal structure of 2 was determined by X-ray diffraction analysis. The copper atom has a distorted square-planar environment; the ! angle between the CuN2 and CuBr2 planes is 37.004 degrees. The calculated omega parameters for optimized structures 1 and 2 were 76.002 degrees and 43.949 degrees, indicating significant deviations from the ideal tetrahedral and square-plane geometries, respectively. Molecules 2 form dimers due to non-covalent Cu center dot center dot center dot Br contacts, which were analyzed by DFT calculations. The complexes were also characterized by cyclic voltammetry and UV-Vis spectroscopy. A quasi-reversible Cu(II)/Cu(I) redox event with E1/ 2 potentials of 0.81 and 0.66 V (vs. SHE) was found for 1 and 2, respectively. The electronic absorption spectra showed the presence of Cu(I) species as a result of the partial reduction of the complexes in the acetonitrile solution. Both complexes were tested as homogenous catalysts for the oxidation of isopropylbenzene (IPB) in acetonitrile at low temperatures. Differences in the mechanism of the catalytic reaction and the composition of the reaction products depending on the oxidizing ability of the catalyst were revealed.

Automated summary

Two new isomeric complexes [CuBr2(R-bian)] (R=4-Me-Ph (1), 2-Me-Ph (2)) were synthesized and characterized. Crystal structure analysis revealed a distorted square-planar environment around the copper atom, with a significant deviation from ideal tetrahedral and square-plane geometries in complexes 1 and 2, respectively. Dimer formation through non-covalent Cu center dot center dot center dot Br interactions was observed in complex 2. Cyclic voltammetry and UV-Vis spectroscopy showed a quasi-reversible Cu(II)/Cu(I) redox event and the presence of Cu(I) species in solution. Both complexes exhibited catalytic activity for the oxidation of isopropylbenzene, with differences in the reaction mechanism and product composition depending on the oxidizing ability of the catalyst.