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

Guilherme Cariello; Lucas A Zeoly; Bruno A Piscelli; Thomas Lectka; Rodrigo A Cormanich

doi:10.1039/d3cc05389j

The pitfalls of using J_HF spin-spin coupling constants to infer hydrogen bond formation in organofluorine compounds

Chem Commun (Camb). 2023 Dec 12;59(99):14661-14664. doi: 10.1039/d3cc05389j.

Authors

Guilherme Cariello¹, Lucas A Zeoly¹, Bruno A Piscelli¹, Thomas Lectka², Rodrigo A Cormanich¹

Affiliations

¹ Universidade Estadual de Campinas (UNICAMP), Instituto de Química, Monteiro Lobato Street, Campinas, Sao Paulo 13083-862, Brazil. cormanich@unicamp.br.
² Department of Chemistry, Johns Hopkins University, 3400 North Charles St., Baltimore, MD, 21218, USA. lectka@jhu.edu.

PMID: 37987509
DOI: 10.1039/d3cc05389j

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.