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

Autor(es)

Zeoly, Lucas A. ^[1] ; Coelho, Fernando ^[1] ; Cormanich, Rodrigo A. ^[1]

Afiliação do(s) autor(es)

^[1] Inst Chem, Dept Organ Chem, BR-13083970 Campinas, SP - Brazil

• Tipo de documento: Artigo Científico
• Fonte: Journal of Physical Chemistry A; v. 123, n. 46, p. 10072-10078, NOV 21 2019.
• Citações Web of Science: 0

Resumo

The intramolecular CF center dot center dot center dot HX. (X = O or S) H-bond and J(FH) spin-spin coupling constants (SSCCs) in 2-fluorophenol and 2-fluorothiophenol were investigated experimentally by H-1 and F-19 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 J(HF) SSCC in 2-fluorophenol has its origin on LP(F)/sigma(OH) steric interactions and should be labeled as (4TS)J(HF). On the other hand, the analogue SSCC for 2-fluorothiophenol has its origin on the intramolecular H-bond LP(F) -> sigma(SH){*} hyperconjugative interaction and should be described as a (1h)J(FH) SSCC. (AU)

• Processo FAPESP: 18/03910-1 - Estudos físico-químicos de compostos orgânicos fluorados: abordagens experimental e teórica
• Beneficiário: Rodrigo Antonio Cormanich
• Modalidade de apoio: Auxílio à Pesquisa - Jovens Pesquisadores