Gold(I) α‐Trifluoromethyl Carbenes: Synthesis, Characterization and Reactivity Studies
Mathilde Rigoulet, David Vesseur, Karinne Miqueu, Didier Bourissou
Abstract
Abstract 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 .
Topics & Concepts
CarbeneChemistryTrifluoromethylReactivity (psychology)ArylSubstituentElectrophileTrifluoromethylationLigand (biochemistry)Nuclear magnetic resonance spectroscopyTransition metal carbene complexMedicinal chemistryCatalysisStereochemistryOrganic chemistryAlkylBiochemistryPathologyReceptorMedicineAlternative medicineCyclopropane Reaction MechanismsFluorine in Organic ChemistryCatalytic Alkyne Reactions