We have tested the fragmentations of [LnAu III X2] + with a series of monodentate-, bidentate-and tridentate ligands with N, P, and S coordinating atoms (Table ). The monodentate ligands do not support the desired formation of gold(II) complexes. The reason stems from the coordination flexibility of the monodentate ligands in the coordination sphere of the gold atom. The gold(III) precursors were formed in a square planar geometry with the [( 1 -ligand)2Au III X2] + speciation. These complexes can easily eliminate the dihalogen molecule (X2) because the resulting [( 1ligand)2Au I ] + can attain the favoured linear arrangement of the two  1 -ligands and thereby make Reaction 2 favoured. On the contrary, the bidentate ligands do support the formation of gold(II) complexes. The gold(III) precursors were formed with the [( 2 -Ligand)Au III X2] + speciation. Fragmentation of the gold(III) precursors with N,N-bidentate ligands led almost exclusively to the elimination of a halogen radical and thus to the formation of the desired [( 2 -ligand)Au II X] + complexes (Reaction 1, Figure ). In comparison, phosphine-based ligands are less suitable for preparation of gold(II) complexes because they get easily oxidised in the presence of the gold(III) salts. Accordingly, next to the desired gold(III) precursors with the bis-phosphine ligands (P,P-Ligands), we have always observed gold(I) complexes with the bis-phosphine-oxide ligands. Nevertheless, we have detected a fraction of the desired [(P,P-Ligand)Au III X2] + precursors with the bis-diphenylphosphine ethylene (dppe) and propylene (dppp) ligands and therefore we could explore the possibility to form the gold(II) complexes. The desired Reaction 1 occurred only for complexes with X = Br; hence, we observed the formation of [(dppe)Au II Br] + and [(dppp)Au II Br] + . The competing reactions led generally to the reduction of the complexes to the gold(I) state and to a degradation of the ligands (see Table , and the Supporting Information). The bis(diphenylphosphino)methane (dppm) ligand with a smaller bite angle provided directly just gold(I) complexes. We also tested sulphur-based ligands but were unable to detect any desired gold(III) precursor complexes.