Non-bonding interactions and non-covalent delocalization effects play a critical role in the relative stability of group 12 complexes arising from interaction of diethanoldithiocarbamate with the cations of transition metals Zn(II), Cd(II), and Hg(II): a theoretical study

The chelating properties of diethanoldithiocarbamate (DEDC) and π-electron flow from the nitrogen atom to the sulfur atom via a plane-delocalized π-orbital system (quasi ring) was studied using a density functional theory method. The molecular structure of DEDC and its complexes with Zn(II), Cd(II), and Hg(II) were also considered. First, the geometries of this ligand and DEDC-Zn(II), DEDC-Cd(II), and DEDC-Hg(II) were optimized, and the formation energies of these complexes were then calculated based on the electronic energy, or sum of electronic energies, with the zero point energy of each species. Formation energies indicated the DEDC-Zn(II) complex as the most stable complex, and DEDC-Cd(II) as the least stable. Structural data showed that the N1–C2 π-bond was localized in the complexes rather than the ligand, and a delocalized π-bond over S7–C2–S8 was also present. The stability of DEDC-Zn(II), DEDC-Cd(II), and DEDC-Hg(II) complexes increased in the presence of the non-specific effects of the solvent (PCM model), and their relative stability did not change. There was π-electron flow or resonance along N1–C2–S7 and along S7–C2–S8 in the ligand. The π-electron flow or resonance along N1–C2–S7 was abolished when the metal interacted with sulfur atoms. Energy belonging to van der Waals interactions and non-covalent delocalization effects between the metal and sulfur atoms of the ligand was calculated for each complex. The results of nucleus-independent chemical shift (NICS) indicated a decreasing trend as Zn(II)?<?Cd(II)?<?Hg(II) for the aromaticity of the quasi-rings. Finally, by ignoring van der Waals interactions and non-covalent delocalization effects between the metal and sulfur atoms of the ligand, the relative stability of the complexes was changed as follows:

$$ \mathrm{DEDC}-\mathrm{Z}\mathrm{n}\left(\mathrm{I}\mathrm{I}\right)>\mathrm{DEDC}-\mathrm{C}\mathrm{d}\left(\mathrm{I}\mathrm{I}\right)>\mathrm{DEDC}-\mathrm{H}\mathrm{g}\left(\mathrm{I}\mathrm{I}\right) $$

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Graphical Abstract Huge electronic cloud localized on Hg(II) in the Hg(II)-DEDC complex