Density functional theory investigation of the binding interactions between phosphoryl, carbonyl, imino, and thiocarbonyl ligands and the pentaaqua nickel(II) complex: Coordination affinity and associated parameters

Density Functional Theory (UB3LYP/6-311++G(d,p)) calculations of the affinity of the pentaaqua nickel(II) complex for a set of phosphoryl [Oï£P(H)(CH3)(PhR)], imino [HNï£C(CH 3)(PhR)], thiocarbonyl [Sï£C(CH3)(PhR)] and carbonyl [Oï£C(CH3)(PhR)] ligands were performed, where Rï£NH2, OCH3, OH, CH3, H, Cl, CN, and NO2 is a substituent at the para-position of a phenyl ring.The affinity of the pentaaqua nickel(II) complex for these ligands was analized and quantified in terms of interaction enthalpy (ΔH), Gibbs free energy (ΔG298), geometric and electronic parameters of the resultant octahedral complexes. The ΔH and ΔG298 results show that the ligand coordination strength increases in the following order: carbonyl < thiocarbonyl < imino < phosphoryl. This coordination strength order is also observed in the analysis of the metal-ligand distances and charges on the ligand atom that interacts with the Ni(II) cation. The electronic character of the substituent R is the main parameter that affects the strength of the metal-ligand coordination. Ligands containing electron-donating groups (NH 2, OCH3, OH) have more exothermic ΔH and ΔG298 than ligands with electron-withdrawing groups (Cl, CN, NO2). The metal-ligand interaction decomposed by means of the energy decomposition analysis (EDA) method shows that the electronic character of the ligand modulates all the components of the metal-ligand interaction. The absolute softness of the free ligands is correlated with the covalent contribution to the instantaneous interaction energy calculated using the EDA method. © 2013 Wiley Periodicals, Inc. The interactions between metal cations and biomolecules are extensively studied in bioinorganic and coordination chemistry. Transition metal ions are present in many enzymes, metalloproteins, peptide hormones, and nucleic acids and are fundamental for their biological functions. In this work, the affinity of the pentaaqua nickel(II) complex toward a set of para-substituted ligands is evaluated. The electronic nature of the ligand modulates the magnitude of the electrostatic, covalent, and repulsion components of the interaction. © 2013 Wiley Periodicals, Inc.