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

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posted on 2022-08-03, 19:23 authored by Oriol Planas, Vytautas Peciukenas, Markus Leutzsch, Nils Nöthling, Dimitrios A. Pantazis, Josep Cornella
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 decelerate reductive elimination. On the other hand, a parallel analysis for cationic bismuthonium fluorides revealed the crucial role of tetrafluoroborate anion as fluoride source. Both experimental and theoretical analyses conclude that C–F bond formation occurs through a low-energy five-membered transition-state pathway, where the F anion is delivered to a C­(sp2) center, from a BF4 anion, reminiscent of the Balz–Schiemann reaction. The knowledge gathered throughout the investigation permitted a rational assessment of the key parameters of several ligands, identifying the simple sulfone-based ligand family as an improved system for the stoichiometric and catalytic fluorination of arylboronic acid derivatives.

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