Mechanism of the Aryl-F Bond-Forming Step from Bi(V) Fluorides.

ABSTRACT: In this article, we describe a combined experimental and theoretical mechanistic investigation of the C(sp²)-F bond formation from neutral and cationic high-valent organobismuth(V) fluorides, featuring a dianionic bis-aryl sulfoximine ligand. An exhaustive assessment of the substitution pattern in the ligand, the sulfoximine, and the reactive aryl on neutral triarylbismuth(V) difluorides revealed that formation of dimeric structures in solution promotes facile Ar-F bond formation. Noteworthy, theoretical modeling of reductive elimination from neutral bismuth(V) difluorides agrees with the experimentally determined kinetic and thermodynamic parameters. Moreover, the addition of external fluoride sources leads to inactive octahedral anionic Bi(V) trifluoride salts, which decelerat

SUBMITTER: Planas O 

PROVIDER: S-EPMC9394462 | biostudies-literature | 2022 Aug

REPOSITORIES: biostudies-literature