Enhanced catalytic (ep)oxidation of olefins by VO(II), ZrO(II) and Zn(II)-imine complexes; extensive characterization supported by DFT studies

Three mononuclear di-valent VO2+, ZrO2+ and Zn2+-complexes (VOL, ZrOL and ZnL, respectively) were prepared from asymmetrical di-basic tetradentate di-imine ligand (6,6'-((1E,1'E)-((4-chloro-1,2-phenylene)bis(azaneylylidene))bis(methaneylylidene))bis(2-ethoxy phenol, H2L). To confirm the M-complexes compositions, various spectral tools (FT-IR, EI/M and UV-Vis. spectra), molar conductance, thermal, elemental analysis and pXRD analyses were accomplished. Distorted octahedral geometry was confirmed for ZnL and square pyramidal geometry was elucidated for VOL and ZrOL. Their catalytic efficiency was investigated in the epoxidation of 1,2-cyclohexene by H2O2. They exhibited moderate to excellent catalytic control. The effect of temperature, time, solvent, type of oxidant and amount of catalysts were studied in order to determine the optimal catalytic atmosphere. The catalysts screening for epoxidation of alternative cyclic and acyclic olefins at optimization was reported. The variation of central metal ions from high to low valents (Zr4+, V4+ and Zn2+ ions) and their capability for oxidation control their catalytic potential are the most effective aspects in the epoxidation reaction. The catalytic oxidation of 2-aminothiophene within VOL, ZrOL and ZnL, as a first trial, by H2O2 was examined. Also, QSAR parameters and DFT studies were performed to predict the catalytic properties of VOL, ZrOL and ZnL, to assert on chosen application. Effective surface properties of VO(II) complex were promoted for progressing its catalytic activity, which already happened. The catalytic mechanism was supported by the sequenced stability difference between proposed intermediates based on the difference in their recorded formation energy from the DFT study. (C) 2021 Elsevier B.V. All rights reserved.