Stable N-centered radical complexes

Radical catalysts and earth-abundant metals

Polydentate architectures derived from anilines and o-phenylenediamine are promising candidates to elaborate bio-inspired catalysts. Indeed, once deprotonated and coordinated to a metal center under aerobic conditions, those ligands give access to stable radical complexes. Our work aims at understanding the reactivity and the catalytic activity of unprecedented species, applied to various synthetic transformations.



We recently developed the first cobalt catalyzed intramolecular oxy-carbonylation of alkynoic acids, thanks to the design of a unique diradical cobalt(III) complex. The reaction proceeds smoothly, without any additives. The methodology was successfully applied to 14 substrates. The cobalt catalyst is air- and moisture-stable and was found more active than most of the catalytic systems based on noble metals. 

O₂ as a green oxidant / O-atom source

Polydentate architectures derived from anilines and o-phenylenediamines are under-exploited, mainly due to their facile oxidation. Nevertheless, this feature is particularly attractive for a catalytic application that could benefit from O₂. Our efforts are directed towards the design of renewable radical catalysts that could activate and use O₂ in oxidation/oxygenation reactions.