DFT analysis of the interaction between Hg2+ and monodentate neutral ligands using NBO, EDA, and QTAIM

We report thermodynamic, geometric, and electronic parameters for the interaction between neutral ligands and the [Hg(H 2 O)] 2+ dication, using the B3LYP/6–311 + G(d,p) approach. Gibbs free energies for the interaction were employed to rank the affinity order of the several neutral ligands. To iden...

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Bibliographic Details
Published in:Journal of molecular modeling 2020-05, Vol.26 (6), p.146-146, Article 146
Main Authors: da Silva, Victor Hugo Malamace, de Mesquita Carneiro, José Walkimar, da Costa, Leonardo Moreira, Ferreira, Glaucio Braga
Format: Article
Language:English
Subjects:
Affinity
Aldehydes
Amides
Ammonia
Carboxylic acids
Characterization and Evaluation of Materials
Chemistry
Chemistry and Materials Science
Computer Appl. in Life Sciences
Computer Applications in Chemistry
Gibbs free energy
Interaction parameters
Ligands
Mercury (metal)
Molecular Medicine
Original Paper
Parameter identification
Phosphine oxide
Theoretical and Computational Chemistry
Thiocyanates
Water chemistry
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Summary:We report thermodynamic, geometric, and electronic parameters for the interaction between neutral ligands and the [Hg(H 2 O)] 2+ dication, using the B3LYP/6–311 + G(d,p) approach. Gibbs free energies for the interaction were employed to rank the affinity order of the several neutral ligands. To identify the parameters that characterize the affinity between the two fragments, the metal-ligand interaction was analyzed according to the EDA, NBO, and QTAIM decomposition schemes. The phosphine oxide showed the highest affinity for the Hg(H 2 O) 2+ dication, mainly due to the P=O bond polarization. Ligands containing the sulfur atom, characterized by a high covalent component for the metal-ligand interaction, are the following in the interaction order. According to the Gibbs free energy for substitution of one water molecule in the [Hg(H 2 O) 2 ] 2+ complex, the sequence for the affinity order is: phosphine oxide > thioketone > thioesther > lactam > amide > amine > carboxylic acid > thiophene > ketone > esther > thiol > thiocyanate > ammonia > disulfide > aldehyde > ether > haloydrin > alcohol > enol > azide. Graphical abstract Synopsis The interaction between the Hg 2+ cation and monodentate ligands containing S, O, or N atoms was evaluated in terms of energetic (bond strength, electrostatic and covalent interactions, donation energy), geometric (metal-ligand distance), electronic (atomic charges, orbital overlap, orbital hybridization) and topologic parameters.
ISSN:1610-2940
0948-5023
DOI:10.1007/s00894-020-04413-5