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submitted on 24.08.2019 and posted on 26.08.2019by Oriol Planas, Feng Wang, Markus Leutzsch, Josep Cornella
The ability of bismuth to maneuver between different oxidation states in a catalytic redox cycle, mimicking the canonical organometallic steps associated to a transition metal, is an elusive and unprecedented approach in the field of homogeneous catalysis. Herein we present a catalytic protocol based on bismuth, a benign and sustainable main-group element, capable of performing every organometallic step in the context of oxidative fluorination of boron compounds; a territory reserved to transition metals. A rational ligand design featuring hypervalent coordination together with a mechanistic understanding of the fundamental steps, permitted a catalytic fluorination protocol based on a Bi(III)/Bi(V) redox couple, which represents a unique example where a main-group element is capable of outperforming its transition metal counterparts. A main text and supplementary material have been attached as pdf files containing all the methodology, techniques and characterization of the compounds reported.