Intramolecular H-Bond Is Formed in 2-Fluorophenol and 2-Fluorothiophenol, but It May Not Be the Main Pathway of the JFH Coupling Constant Transmission.

The intramolecular CF···HX (X = O or S) H-bond and JFH spin-spin coupling constants (SSCCs) in 2-fluorophenol and 2-fluorothiophenol were investigated experimentally by 1H and 19F NMR and theoretically in the framework of the natural bond orbital analysis. In contrast with recent findings from the literature, the results obtained in this work showed that an intramolecular H-bond is formed in the cis conformers and that it has an electrostatic origin. Such an intramolecular electrostatic H-bond is the interaction that rules the conformational preferences on these compounds. Moreover, the natural J-coupling analysis indicated that the JHF SSCC in 2-fluorophenol has its origin on LP(F)/σOH steric interactions and should be labeled as 4TSJHF. On the other hand, the analogue SSCC for 2-fluorothiophenol has its origin on the intramolecular H-bond LP(F) → σSH* hyperconjugative interaction and should be described as a 1hJFH SSCC.