DFT Study of The Interaction between the Ni2+ and Zn2+ Metal Cations and The 1,2-Dithiolene Ligands: Electronic, Geometric and Energetic Analysis

Abstract

Density functional theory (DFT) (B3LYP/6-311++G(d,p)) calculations of the interacting strength 1,2-dithiolene anionic ligands with the [M(OH 2 ) 4 ] 2+ and [M(OH 2 ) 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(OH 2 ) 6 ] 2+ by a dithiolene anionic ligand (L 2− ) and the second is the substitution of two water molecules from the [M(OH 2 ) 4 L] 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.DFT Study of the Interaction between the Ni 2+ and Zn 2+ Metal Cations and the 1,2-Dithiolene Ligands J. Braz. Chem. Soc. 1162

Synthesis, characterization, and thermal and computational investigations of the l-histidine bis(fluoride) crystal

“…These parameters indicate that the formation of the ionic associate is exothermic and spontaneous, at room temperature. The spontaneous association is attributed to the formation of a network of strong hydrogen bonds between the protonated histidine and the fluoride anion [ 31 , 59 , 60 ].…”

“…Petrosyan et al [26] reported that the N(imidazole)-F(fluoride) distances are 2.5421( 16) Å and 2.5269(15) Å, and that the dihedral angle between the main chain carbon atoms of imidazole is −171.85( 12 formation of the ionic associate is exothermic and spontaneous, at room temperature. The spontaneous association is attributed to the formation of a network of strong hydrogen bonds between the protonated histidine and the fluoride anion [31,59,60].…”

Generalized Kohn‐Sham energy decomposition analysis and its applications

“…Metal‐ligand interactions play important roles in nanocrystals, molecular recognition, drug design, metalloprotein chemistry, and so on. Both GKS‐EDA and LMO‐EDA have been employed in the interpretations of various metal‐ligand interactions, which are not trivial tasks due to the inherent complexity of the arrangement of electrons in d‐ and f‐metal‐atom orbitals coupled with the various ligands.…”