High-Valent Fluorinated TM Complexes for Trifluoromethylation (TM = Ni, Cu, Ag)

Noel Nebra
Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA, UMR CNRS 5069), Toulouse, France

Mercredi 2 juillet 2025, 11H00
Bibiothèque du LCT, Couloir 12-13, 4^ème étage, Campus Pierre et Marie Curie

Fluorine atoms drastically affect the biological properties of organic synthons,[1] with the trifluoromethyl group occupying a preferential place in drug and agrochemical design. The creation of C-CF₃ bonds via cross-coupling reactions thus represents an appealing strategy to build molecular complexity. In marked contrast, unfortunately, the C-CF₃ bond formation via reductive elimination (R.E.) from well-defined [R-TM-CF₃] fragments remains a challenging task. An original approach to circumvent this bottleneck resides in the building of high-valent [R-TM-CF₃] organometallics, which are more prone to get reduced and may eventually lead to the key R.E. step easier (Figure 1). In this communication, an expeditious entry to high oxidation state MCF₃ compounds (M = Ni^IV, Cu^III, Ag^III), together with their application in trifluoromethylation and C-heteroatom bond formation, will be disseminated.[2-4] More precisely, this seminar deals with the authentication of MCF species, alongside their crucial role in trifluoromethylation reactions via uncommon 2e_- redox shuttles. The singular bonding of high-valent MCF₃ complexes displaying an Inverted Ligand Field (ILF) electronic structure [5] will be briefly discussed, and unprecedented reactivity studies supporting this ILF electronic structure will be presented.

[Picture]

Figure 1. Guiding principle of this talk: Synthesis of high oxidation state MCF3 complexes via 2e^- oxidation step and subsequent use for synthetic purposes (trifluoromethylation).

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References :
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