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Synthesis, structural characterization, catalytic activity, and DFT studies of Cu(II) and Ni(II) Schiff base complexes for CO2 cycloaddition to cyclic carbonates

  • Ayşe Kazanci Dağ,
  • Ayşegül Köse,
  • Emine Aytar,
  • Akın Ozkan,
  • Muhammet Köse

摘要

In this study, two novel Schiff base ligands (HA and HB) and their corresponding Cu(II) and Ni(II) complexes namely [Cu(A)2], [Ni(A)2], [Cu(B)2] and [Ni(B)2] were synthesized. The resulting compounds were comprehensively characterized using elemental analysis, Fourier-transform infrared (FT-IR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, molar conductivity measurements, and single-crystal X-ray diffraction. Density functional theory (DFT) calculations were performed at the B3LYP/6-311 + + G(d, p) level of theory to optimize molecular geometries, investigate keto-enol tautomerism, and evaluate the nonlinear optical (NLO) properties of the systems. Furthermore, the catalytic activity of the complexes was assessed for the solvent-free cycloaddition of carbon dioxide (CO2) with epoxides under high-pressure conditions. Among the catalysts tested, the [Ni(A)2]/DMAP system exhibited the highest performance and selectivity toward cyclic carbonate formation under optimized reaction conditions.