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12:59
A Study of the Complexation of Mercury(II) with Dicysteinyl Tetrapeptides by Electrospray Ionization Mass Spectrometry
Published on: January 8, 2016
Chalcogenophilicity of mercury
Abu Md Asaduzzaman1, Georg Schreckenbach
1Department of Chemistry, University of Manitoba, Winnipeg, Manitoba R3T 2N2, Canada. asaduzza@cc.umanitoba.ca
Inorganic Chemistry
|March 17, 2011
Summary
Density-functional theory (DFT) calculations reveal mercury's (Hg) chalcogenophilicity. Ligand electronegativity and metal oxidation state influence Cd and Hg bonding, with Hg-S bonds exhibiting the highest bond dissociation energy (BDE).
Area of Science:
- Inorganic Chemistry
- Computational Chemistry
- Materials Science
Background:
- Recent studies have highlighted the chalcogenophilicity of mercury (Hg).
- Understanding the bonding characteristics of cadmium (Cd) and Hg is crucial in coordination chemistry.
Purpose of the Study:
- To investigate the chalcogenophilicity of mercury (Hg) using density-functional theory (DFT).
- To explore the influence of ligand nature and metal oxidation state on Cd and Hg bonding.
- To analyze the factors affecting Hg-chalcogen bond distances and strengths.
Main Methods:
- Density-functional theory (DFT) calculations were employed.
- A range of molecules were studied, including ME, [M(EH)(4)](n), M(SH)(3)EH, and [Tm(Y)]MEZ complexes.
- Analysis of bond distances, bond types (ionic vs. covalent), and bond dissociation energies (BDE) was performed.
Main Results:
- Bonding in Cd and Hg complexes is dependent on metal oxidation state and ligand electronegativity.
- More electronegative ligands favor ionic bonding, while less electronegative ligands favor covalent bonding.
- Hg-S bonds demonstrated the highest bond dissociation energy (BDE), followed by Hg-Se and Hg-Te, irrespective of the complex type.
Conclusions:
- DFT calculations provide insights into Hg chalcogenophilicity and Cd/Hg bonding.
- Ligand properties and metal characteristics dictate the nature and strength of metal-ligand bonds.
- The observed Hg-chalcogen bond distances are influenced by electronegativity, crystal packing, and steric effects.
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