The pitfalls of using JHF spin–spin coupling constants to infer hydrogen bond formation in organofluorine compounds

Abstract

Theoretical decomposition of “through space” spin–spin coupling constants (SSCCs) in organofluorine compounds signal that intramolecular hydrogen bonds (H-bonds) are not the primary mechanism of transmission for SSCCs. Increasing solvent polarity may disrupt H-bonds, but not necessarily the J_FH SSCC. Substituent effects may drastically alter the SSCC transmission pathway. Accurate SSCC analysis requires benchmarking theoretical calculations to support experimental data interpretation.