Gold(I) α‐Trifluoromethyl Carbenes: Synthesis, Characterization and Reactivity Studies

International audienceAryl trifluoromethyl diazomethanes 2-R (R = Ph, OMe, CF 3) are readily decomposed by the (o-carboranyl)diphosphine gold(I) complex 1. The resulting α-CF 3 substituted carbene complexes 3-R have been characterized by multi-nuclear NMR spectroscopy as well as X-ray crystallography (for 3-Ph). The bonding situation was thoroughly assessed by computational means, showing stabilization of the electrophilic carbene center by π-donation from the aryl substituent and backdonation from Au, as enhanced by the chelating P^P ligand. Reactivity studies under stoichiometric and catalytic conditions substantiate typical carbene-type behavior for 3-Ph