We report on a comprehensive reactivity study starting from [AuF(3) (SIMes)] to synthesize different motifs of monomeric gold(III) fluorides. A plethora of different ligands has been introduced in a mono-substitution yielding trans-[AuF(2) X(SIMes)] including alkynido, cyanido, azido, and a set of perfluoroalkoxido complexes. The latter were better accomplished via use of perfluorinated carbonyl-bearing molecules, which is unprecedented in gold chemistry. In case of the cyanide and azide, triple substitution gave rise to the corresponding [AuX(3) (SIMes)] complexes. Comparison of the chemical shift of the carbene carbon atom in the (13) C(1) H NMR spectrum, the calculated SIMes affinity and the Au-C bond length in the solid state with related literature-known complexes yields a classification of trans-influences for a variety of ligands attached to the gold center. Therein, the mixed fluorido perfluoroalkoxido complexes have a similar SIMes affinity to AuF(3) with a very low Gibbs energy of formation when using the perfluoro carbonyl route.