Multimodal S(VI) Exchange Click Reactions Derived from SF₂ Moieties: Comparative Kinetics and Stereochemistry of SuFEx and SuPhenEx Reactions.

ABSTRACT: The reaction mechanism of multimodal SuFEx and SuPhenEx click chemistries was investigated in detail for substitution of both the first and second fluoride or p-nitrophenolate leaving groups in ∼RN = SOF₂ and RN = SOF(p-NO₂-phenol) substrates by temperature-dependent kinetics and density functional theory (DFT) calculations. Both the DFT calculations and the experimentally derived ΔH^‡ indicate relatively small values for the activation enthalpies (4-15 kcal/mol), but almost constant and significant values of -TΔS₂₅^‡ (10-14 kcal/mol). This indicates that depending on the precise nucleophile and S(VI) core, the reaction is either controlled by a mixture of enthalpy and entropy or basically is dominated

SUBMITTER: Zhu Y 

PROVIDER: S-EPMC12305642 | biostudies-literature | 2025 Jul

REPOSITORIES: biostudies-literature