A DFT study of the interaction between [Cd(H 2 O) 3 ] 2+ and monodentate O-, N-, and S-donor ligands: bond interaction analysis.

A series of B3LYP/6-311+G(d,p) calculations of the affinity of monodentate ligands for [Cd(H2 O)3 ]2+ are performed. Three types of ligands containing O (phosphine oxide, lactam, amide, carboxylic acid, ester, ketone, aldehyde, ether, halohydrin, enol, furan), N (thiocyanate, amine, ammonia, azide), and S (thioester, thioketone, thiol, thiophene, disulfide) interacting atoms are investigated. The results show that phosphine oxide has the largest affinity for the cadmium cation due to the polarization of the P=O bond. As the P atom has a large atomic radius, the O atom can polarize the electronic cloud enhancing its amount of electronic charge and favoring the interaction with Cd2+ . The affinity order found is phosphine oxide > thioester > lactam > amide > carboxylic acid > ester > thioketone > ketone > thiocyanate > amine > ammonia > aldehyde > ether > thiol > thiophene > enol > halohydrin > disulfide > azide > furan ligands. These results were also corroborated by the functional M06-2X. The electronic effects (resonance and induction) of neighboring groups of the interacting atom modulate the strength of metal-ligand binding. For almost all the O-donor ligands the electrostatic component has the same magnitude as the covalent term, while for the N- and S-donor ligands the covalent term is predominant. The polarization term accounts for twice the exchange term as part of the covalent component. The dispersion term varies less than 2 kcal mol-1 for the complexes analyzed. The Pauli repulsion term is correlated with the metal ligand distance, increasing in the compounds with decreased metal-ligand bond length. The charge between the interacting atoms is also strongly correlated with both the interacting strength and the electrostatic interaction component. The natural bond orbital analysis highlights correlations of the bond order, and S and P contributions of the interacting metal-ligand orbital with the coordination strength. Graphical abstract The affinity of 20 monodentate ligands with different functional groups for the [Cd(H2 O)3 ]2+ cation is calculated based on the interaction enthalpy and Gibbs free energy for the substitution of one water molecule from the fully hydrated cation. The affinity is correlated with geometric, electronic, and energetic parameters of the ligands and the complexes as well as with energy decomposition and natural bond order analyses results.