Structural, Spectral (IR and UV/Visible) and Thermodynamic Properties of Some 3d Transition Metal(II) Chloride Complexes of Glyoxime and Its Derivatives: A DFT and TD-DFT Study

Abstract

Metal complexes bearing vic-dioxime ligands have been extensively used as analytical and biochemical reagents, and are well-known antimicrobial agents. Herein is reported a DFT study on the molecular structures, thermodynamic properties, chemical reactivity and spectral properties of some 3d metal(II) chloride complexes of glyoxime. The functionals B3LYP and CAM-B3LYP have each been used in conjunction with LANL2DZ for the metal(II) ions (Fe 2+ , Co 2+ , Ni 2+ and Cu 2+ ) and the Poplestyle basis set 6-31G+(d,p) for the rest of the elements, to perform theoretical calculations. The metal complexation abilities of the glyoxime ligands studied in this work have been evaluated on the basis of metal-ligand binding energies. These ligands were found to have high affinities towards Ni(II) and Fe(II) ions, and all complexation reactions were found to be thermodynamically feasible. Ligand-to-metal electron donations in the complexes studied have been revealed by natural population analysis. The fully optimized geometries of the complexes have adopted square planar structures around the central metal ions. On the basis of orbital composition analysis, the UV-Vis electronic absorption bands of these molecules have been attributed mainly to MLCT, LMCT and d-d electronic transitions involving metal-based orbitals.

Synthesis, characterization, thermal, anticancer studies, and density functional theory for potentially active pyrimidine‐based complexes

“…The initial geometry of the ligand and all complexes using the CAM‐B3LYP/LanL2DZ basis set for all atoms had been optimized to validate the experimental results 18,19 . In the optimized geometries, energy minima were confirmed by frequency calculations, and only real frequencies were found confirming the optimized geometries as minima on their potential energy surfaces.…”

Syntheses and Structural Investigations of Penta-Coordinated Co(II) Complexes with Bis-Pyrazolo-S-Triazine Pincer Ligands, and Evaluation of Their Antimicrobial and Antioxidant Activities

“…The structure of complex 2 was optimized in the gas phase using the B3LYP method employing 6-31G(d,p) for nonmetal atoms and LANL2DZ for Co [65] with the aid of Gaussian 09 software [66]. All frequency results are positive and no imaginary frequency indicating real minima.…”

Influence of Multiplicity on Properties of Ndx (X= 6, 7 and 8) Halide Transition Metal(Ii) Complexes of Glyoxime Ligand in Gas Phase and Aqueous Solution: Computational Assessment

“…But, the careful survey of the computational literature displayed few researches on this point [13][14]. In sake of the continuation, structural, spectral and thermodynamic properties of 3 rd row transition metal (II) chloride complexes of glyoxime and its derivatives were investigated by the mean of computational tools ( DFT and TD-DFT) [15]. Higher affinity of these ligands towards Ni (II) and Fe (II) and the thermodynamical feasibility of all complex reactions have been revealed.…”