LAUSR

A theoretical investigation of the binding ability of different ligands [L = CO, H2O, H2S, N2, NH3, 1,3-dimethylimidazole (DMI), C2H2 and C2H4] with metal isocyanide and cyanide (MNC and MCN; M = Cu, Ag, Au) compounds has been carried out using quantum chemical computations. In order to analyze the thermochemical stability of these complexes, we have calculated the changes in the related dissociation energies and free energies by considering different possible dissociation pathways (four two-body and one three-body) such as (a) LMCN(/NC) = L + MCN(/NC); (b) LMCN = LM + CN; (c) LMCN = L + M + CN; (d) LMCN = LM+ + CN−; and (e) LMCN = L− + MCN+. The possible dissociation processes are endothermic in nature at room temperature suggesting non-spontaneity at 298 K. Our inspection suggests that MNC have higher binding ability than the MCN compounds in all of the L-bonding cases and both of them follow similar trends as Au > Cu > Ag. The natural bond orbital analysis, topological analysis of the electron density from atoms in molecules technique, and energy decomposition analysis have been carried out to characterize the nature of interaction between L and MCN which shows that the L‐M bonds acquire some degree of covalent character. Furthermore, in order to check the validity of the conceptual DFT-based electronic structure principles like maximum hardness and minimum electrophilicity principles, the change in the relevant global reactivity descriptors like chemical hardness (η), chemical potential (μ), and electrophilicity index (ω) is also studied along the isomerization path, LMNC → LMCN.