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

Aryl 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.