Gold(I) Fluorohalides: Theory and Experiment

The anionic trifluoromethylgold(I) derivatives [CF3AuX]−, which have been prepared and isolated as their [PPh4]+ salts in good yield, undergo thermally induced difluorocarbene extrusion in the gas phase, giving rise to the mixed gold(I) fluorohalide complexes [F−Au−X]− (X=Cl, Br, I). These triatomic species have been detected by tandem mass spectrometry (MS2) experiments and their properties have been analyzed by DFT methods. The CF2 extrusion mechanism from the Au−CF3 moiety serves as a model for the CF2 insertion into the Au−F bond, since both reactivity channels are connected by the microreversibility principle. Full house for gold: The whole series of mixed gold(I) fluorohalides [F−Au−X]− is formed by thermally induced difluorocarbene extrusion from the anionic [CF3AuX]− derivatives in the gas phase.