Tuning the Nucleophilicity and Electrophilicity of Group 10 Elements through Substituent Effects: A DFT Study

In this study, a series of electron donor (–NH(2), –NMe(2) and –(t)Bu) and electron-withdrawing substituents (–F, –CN and –NO(2)) were used to tune the nucleophilicity or electrophilicity of a series of square planar Ni(2+), Pd(2+) and Pt(2+) malonate coordination complexes towards a pentafluoroiodobenzene and a pyridine molecule. In addition, Bader’s theory of atoms in molecules (AIM), noncovalent interaction plot (NCIplot), molecular electrostatic potential (MEP) surface and natural bond orbital (NBO) analyses at the PBE0-D3/def2-TZVP level of theory were carried out to characterize and discriminate the role of the metal atom in the noncovalent complexes studied herein. We hope that the results reported herein may serve to expand the current knowledge regarding these metals in the fields of crystal engineering and supramolecular chemistry.