• Nickel(II) cation;
  • metal–ligand interaction;
  • substituent effect;
  • DFT;
  • EDA

Density Functional Theory (UB3LYP/6-311++G(d,p)) calculations of the affinity of the pentaaqua nickel(II) complex for a set of phosphoryl [O[DOUBLE BOND]P(H)(CH3)(PhR)], imino [HN[DOUBLE BOND]C(CH3)(PhR)], thiocarbonyl [S[DOUBLE BOND]C(CH3)(PhR)] and carbonyl [O[DOUBLE BOND]C(CH3)(PhR)] ligands were performed, where R[DOUBLE BOND]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 (NH2, 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.