Two new square planar Cu(II) and Ni(II) complexes, [CuL 1 (NCO)] (1) and [NiL 2 (N 3 )] (2) have been synthesized with two different tridentate N 2 O donor Schiff base ligands L 1 H (1:1 condensation product of benzoylacetone and 2-diethylaminoethylamine) and L 2 H (1:1 condensation product of benzoylacetone and 2-dimethylaminoethylamine), respectively. Both the complexes 1 and 2 have been characterized by elemental analysis, IR, UVVis spectroscopy, room temperature magnetic susceptibility measurement, electrochemical, thermal, and single crystal X-ray diffraction studies. Structural studies reveal that in both the complexes metal centers have square planar environment with N 2 O donor set of Schiff base ligands and terminal pseudohalide anions (isocyanate for 1 and azide for 2) at four coordination sites of square plane.
Two new dinuclear bis(μ2-phenoxo)-bridged copper(ii) complexes [Cu(NCS)L1]2 (1) and [Cu(NCS)L2]2 (2) have been synthesized using two tridentate NNO-donor Schiff-base ligands, L1H (Me2N(CH2)3N=CHC6H3(OMe)(OH)) and L2H (Me2N(CH2)3N=C(CH3)C6H4(OH)), respectively. They have been characterized by elemental analyses, IR, UV-visible, and electron paramagnetic resonance (EPR) spectroscopy, cyclic voltammetry, and magnetic susceptibility measurements. X-Ray single-crystal structures reveal a central Cu2O2 core in each complex with an isothiocyanate ligand coordinated terminally to each metal centre. The coordination environments around the CuII ions in 1 and 2 are a distorted trigonal bipyramid and a quasi-regular square pyramid, respectively, with significant differences in the Cu–O–Cu bridging angles (100.22(5)° for 1 and 95.64(7)° for 2). Although both CuII dimers present intradimer antiferromagnetic exchange interactions, the magnitudes of the coupling constants in 1 and 2 (J = –119(1) and –0.361(3) cm–1, respectively) are quite different as a result of the different coordination geometries and Cu–O–Cu bridging angles. Both complexes act as promising catalysts or catalyst precursors for the efficient peroxidative oxidation of cycloalkanes (cyclohexane and cycloheptane) to the corresponding cyclic alcohols and ketones, with maximum overall yields of 53% and 56% for 1 and 2, respectively.
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