Complexation of Mono-anionic Bidentate Ligand Dithiocarbamate with σ-Aromatic M3+ Clusters: A DFT Study.

The present study deals with a computational investigation on the role of dithiocarbamate (DTC) anions in the stabilization of σ-aromatic trinuclear mono-cationic metal clusters (M = Cu, Ag and Au). Electrostatic potential, aromaticity, binding energy, thermodynamical parameters and nature of bonding are estimated. Nucleus independent chemical shifts (NICS) and their variants such as NICStotal and FiPC-NICS are employed to calculate aromaticity. The nature of bonding is assessed by the quantum theory of atoms-in-molecules (QT-AIM) and NBO methods. The charge density map in the complex has been assessed by molecular electrostatic potential analysis. Comparison of complexation properties of DTC ligand to common monodentate ligands (pyrazolates, NHC, pyridine, furan and isoxazole) explored in past reveal that DTC anions are more efficient in stabilizing metal complexes. Synopsis. A computational approach is undertaken to investigate complexation properties of dithiocarbamate (DTC) anions with electron-deficient M3+ (M = Cu, Ag & Au) clusters. DTC ligands are found to be efficient chelators as compared to commonly used monodentate ligands to bind and stabilize such unstable trinuclear mono-cationic metal clusters [ABSTRACT FROM AUTHOR]