paper20148

Synthesis, spectral characterization and theoretical investigation of some new

mercury four coordinated complexes

M. Montazerozohori*1, H. Tavakol2, S. Kheiri1, S. A. Musavi1, S. Joohari3

1Department of Chemistry, Yasouj University, Yasouj 75918-74831, Iran

2 Department of Chemistry, Isfahan University of Technology, Isfahan, Iran

3 Department of Basic Science, Yasouj Branch, Islamic Azad University, Yasouj, Iran

Bulgarian Chemical Communications, Volume 46, Number 1 (pp. 96 – 103) 2014

Some new mercury complexes of a bidentate Schiff base ligand with two nitrogen atoms as donor sites have been

prepared and characterized by spectroscopic and analytical studies such as IR, UV-Vis, 1H NMR and 13C NMR,

elemental analysis and molar conductivity. The IR spectrum of ligand showed the characteristic asymmetric and

symmetric vibrations of iminic groups at 1624 and 1620 cm-1 respectively that were unified and shifted by 6-8 cm-1 to

lower energies. The iminic proton signals of ligand were appeared as two doublets at 7.87 and 7.77 ppm that were

downfielded to 7.92-8.91 ppm after coordination to mercury ion in the complexes. The analytical data confirmed 1:1

ratio for ligand to metal salt in all complexes. The structural optimization of ligand and complexes was performed at the

UB3LYP/LANL2MB⁄ level of theory and then some important structural (Bond length(Å), Bond angle(°) and Torsion

angle(°)) and theoretical energetic(HF-Energy, ZPE, ΔE, ΔG, ΔEelectronic and ΔH) data were derived. The bond

lengths(Å) of Hg-N(1) and Hg-N(2) were decreased from from mercury chloride to mercury thiocyante complex and

then decreased in mercury azide complex. The bond angle (°) of N(1)-Hg-N(2) in the complexes was smoothly

increased from mercury chloride to mercury thiocyante complex and then decreased in mercury azide complex. The

opposite of this trend was evaluated for X(1)-Hg-X(2). Accordingly pseudo-tetrahedral geometry was suggested for all

complexes. Therefore the general formula for Hg(II) complexes is MLX2 that in which X= Cl-, Br-, I-, SCN- and N3

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