C(sp3)–F reductive elimination from alkylgold(iii) fluoride complexes

Abstract

Rare examples of C(sp³)–F reductive elimination were observed from several cis-F₂Au(R)(IPr) intermediates generated by oxidation of (IPr)AuR complexes with XeF₂. For R groups bearing β-hydrogens, β-hydride elimination was competitive with C(sp³)–F reductive elimination. For strained cyclic R groups and most acyclic R groups lacking β-hydrogens, carbocation-like rearrangements occurred prior to C(sp³)–F reductive elimination. Kinetics of the decay of one cis-F₂Au(R)(IPr) species, stereochemical analysis of reductive elimination with a chiral R group, and DFT analysis collectively suggest C(sp³)–F reductive elimination proceeding through transient cationic [(IPr)Au(F)(R)]⁺ intermediates with significant ionization of the Au–alkyl bonds.