A [Fe(CB6)] platform for binding of small molecules: Insights from DFT calculations

Abstract

The viability of making [Fe(CB(6))L] (L = H(2), N(2), O(2), nitric oxide [NO(-), NO, and NO(+)], CO(2), and hydrocarbons [CH(4), C(2)H(6), C(2)H(4), and C(6)H(6)]) has been investigated by density functional theory (DFT) calculations. The complexes 2-18 are thermodynamically stable and may be synthesized. The small molecules are activated to some extent after complexation. Molecular orbital and ΔG calculation revealed that the molecular hydrogen and hydrocarbons can be chemically adsorbed and desorbed on [Fe(CB(6))] without any significant chemical modification and therefore [Fe(CB(6))] may serve as a storage material. The N(2), O(2), and nitric oxide (NO(-), NO, and NO(+)) can be activated using [Fe(CB(6))]. Proton, carbon, boron, and nitrogen NMR chemical shift calculation predicts drastic chemical shift difference before and after the complexation of [Fe(CB(6))] with small molecules. This new findings suggest that the CB(6)(2-) ligand-based complex may provide several applications in the future.