The anionic trifluoromethyl-gold(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.