Insights into the Stabilization of Fluoride Ions in Ionic Liquids: Pointers to Better Fluorinating Agents

The fluorination efficiency of a fluorinating agent depends on the free availability of the fluoride ions, which in turn depends on its interaction with its solvation shell. A stable fluoride-based poor solvate ionic liquid (SIL) comprising 1-ethyl-3-methylimidazolium (EMIM) cation and ethylene glycol (EG) was recently reported and demonstrated as a fluorinating agent. Herein, we performed ab initio calculations and ab initio molecular dynamics simulations to gain a microscopic understanding of the intermolecular interactions in this SIL in gas, liquid, and crystalline phases. Ethylene glycol (EG), being capable of forming hydrogen bond(s) with the fluoride ion, prevents the latter from reacting with the EMIM cation. Fluoride forms hydrogen bonds with both the cation and the EG molecule, but it was found to have more affinity toward EG, forming a stronger hydrogen bond with its hydroxyl proton than with the acidic proton of the cation. An optimal concentration of EG in the SIL balances its contribution to stabilizing the fluoride ion and yet making fluoride available for fluorination.