A Computational Scrutiny on the Stability, Structure, and Electronic Features of Alkanesulfonate Based Zincate Salts with Varying Countercations

A systematic computational study has been carried out to investigate the effect of variation of countercations on the structures, stability, and electronic properties of six zincate salts, R(2)ZM [where ZM=[Zn(OSO2Me)(4)](2-); R=Et4N+ (EZM), Et3MeN+ (E3MZM), Et2Me2N+ (E2 M2ZM), EtMe3N+ (EM3ZM), Me4N+ (MZM), and H4N+ (HZM)], based on weakly-coordinating alkanesulfonate ligand. The Computational exploration compared the binding energies (BEs), change in Gibb's free energies (G(form)), HOMO-LUMO energy gaps (HLEGs) and other derived parameters, using B97-D/cc-pVDZ level of study, to investigate the stability pattern, structures, and electronic properties of the cation-anion set of models. The comparative analyses of model salts reveal the stability order as HZM > MZM > EM3ZM > E3MZM > E2 M2ZM > EZM on account of the involved primary and secondary interactions, BEs, and the G(form). Few other important electronic parameters that are closely associated with the chemical reactivity, chemical hardness, chemical potential, and electrophilicity index are highest for HZM salt (most stable), whereas, lowest (least reactive) value was found in case of its dipole moment. The present study on salts based on less explored weakly-coordinating alkanesulfonate ligand would assist in predicting the rational synthesis and design of new metal-containing salts with properties for desired applications.