Exploring alkali metal cation⋯hydrogen interaction in the formation half sandwich complexes with cycloalkanes: a DFT approach

Abstract

Abstract Gas and solvent phase stability of half sandwich complexes between cycloalkanes viz. cyclopropane, cyclobutane, cyclopentane, cyclohexane, bicyclo[2.2.2]octane and adamantane with alkali metal cations (Li+, Na+ and K+) are analysed using density functional theory (DFT). M06-2X/6-31++G(d,p) level is primarily used for the study. The studied half sandwich complexes are stable in gas phase (stabilization energy upto 26.55 kcal mol−1). Presence of solvent phase irrespective of its dielectric, imparts negative impact on the stability of the chosen complexes. The formation of the complexes is exothermic in nature. The process of complexation is both enthalpy (ΔH) and free energy (ΔG) driven. Variation in HOMO (highest occupied molecular orbital) energy also indicates towards the chemical stability of complexes. The interaction is non-covalent with primary contribution from induction component. NBO analysis indicates that C–H bond is the donor and antibonding metal orbital is the acceptor site in the process of complexation. Stability of the complexes depends on the size of the interacting monomers.