C(sp(3))-F reductive elimination from alkylgold(III) fluoride complexes

Rare examples of C(sp(3))-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 beta-hydrogens, beta-hydride elimination was competitive with C(sp(3))-F reductive elimination. For strained cyclic R groups and most acyclic R groups lacking b-hydrogens, carbocation-like rearrangements occurred prior to C(sp(3))-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(sp(3))-F reductive elimination proceeding through transient cationic [(IPr)Au(F)(R)](+) intermediates with significant ionization of the Au-alkyl bonds.