DFT Study of the Interaction between the Ni2+ and Zn2+ Metal Cations and the 1,2-Dithiolene Ligands: Electronic, Geometric and Energetic Analysis
Glauber S. Melengate
Daniel G. S. Quattrociocchi
José M. Siqueira Júnior
Stanislav R. Stoyanov
Leonardo M. Costa
Glaucio B. Ferreira
10.6084/m9.figshare.8194976.v1
https://scielo.figshare.com/articles/dataset/DFT_Study_of_the_Interaction_between_the_Ni2_and_Zn2_Metal_Cations_and_the_1_2-Dithiolene_Ligands_Electronic_Geometric_and_Energetic_Analysis/8194976
<div><p>Density functional theory (DFT) (B3LYP/6-311++G(d,p)) calculations of the interacting strength 1,2-dithiolene anionic ligands with the [M(OH2)4]2+ and [M(OH2)2]2+ complexes (M = Ni and Zn) were performed. Three series of ligands were studied: compounds with an aromatic ring, with an ethylene moiety and with a heterocyclic ring. The ligands have substituents electron donors and acceptors by induction and resonance. Two substitution reactions were studied: the first is the substitution of two water molecules from the [M(OH2)6]2+ by a dithiolene anionic ligand (L2-) and the second is the substitution of two water molecules from the [M(OH2)4L] by another dithiolene anionic ligand. Geometric, electronic and energetic properties of the substituted aquacations are correlated with the metal-ligand affinity. All the substitution processes for both metal cations are spontaneous and are modulated by the electronic effect of each substituent of the ligand. Geometric parameters and chelation angle are correlated with the interaction strength. The energy decomposition analysis (EDA) results show that the electrostatic component is the main stabilizing term for the monosubstituted complexes, while for the disubstituted complexes the covalent term is the main stabilizing component. The polarization term is the main one to describe the covalent character. Natural bond orbital (NBO) shows the acid-base interaction nature of the metal-ligand bond.</p></div>
2019-05-29 02:43:09
divalent metal cations
1,2-dithiolene ligands
DFT
interaction analysis
EDA
NBO