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Experimental and Theoretical Evidence for Nitrogen–Fluorine Halogen Bonding in Silver-Initiated Radical Fluorinations

preprint
submitted on 11.02.2019, 19:03 and posted on 12.02.2019, 15:42 by Ryan Baxter, Alyssa Hua, Sarah Baker, Samantha Bidwell, Hrant Hratchian
We report experimental and computational evidence for nitrogen–fluorine halogen bonding in Ag(I)-initiated radical C–H fluorinations. Simple pyridines form [N–F–N]+ halogen bonds with Selectfluor to facilitate single-electron reduction by catalytic Ag(I). Pyridine electronics affect the extent of halogen bonding, leading to notable differences in selectivity between mono- and bis-fluorinated products. Electronic structure calculations show that halogen bonding to various pyridines alters the single-electron reduction potential of Selectfluor, which is consistent with experimental electrochemical analysis. Multinuclear correlation NMR also provides spectroscopic evidence for pyridine halogen bonding to Selectfluor under ambient conditions.

Funding

56806-DNI6

56225-DNI5

ACI-1429783

CAREER: Mechanistic Study of Radical Initiations for Aromatic Functionalization

Directorate for Mathematical & Physical Sciences

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History

Email Address of Submitting Author

rbaxter@ucmerced.edu

Institution

University of California, Merced

Country

USA

ORCID For Submitting Author

0000-0002-1341-5315

Declaration of Conflict of Interest

No conflict

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