[NBu 4 ][Ag(C 6 F 5 ) 2 ] or [Ag(C 6 F 5 )] act as arylating ligands able to transfer two or one pentafluorophenyl groups to [Tl(C 6 F 5 ) 2 Cl] leading to [NBu 4 ][Tl(C 6 F 5 ) 4 ] (1) and [Tl(C 6 F 5 ) 3 (diox)] (diox=1,4 dioxane) (2) in an improved synthesis, the latter being a starting material for the synthesis of [Tl(C 6 F 5 ) 3 (OPPh 3 )] (3) and [Tl(C 6 F 5 ) 3 (PPh 3 )] (4). However, [Ag(C 6 F 5 )L] does not transfer the pentafluorophenyl group when reacted with [Tl(C 6 F 5 ) 2 Cl] and the complexes [Tl(C 6 F 5 ) 2 Cl(py)] 2 (5), [Tl(C 6 F 5 ) 2 Cl(OPPh 3 )] 2 (6) and [Tl(C 6 F 5 ) 2 (OdppmO) 2 ][Tl(C 6 F 5 ) 2 Cl 2 ] (7) are obtained as the main products, which can be obtained in a better yield by the addition of the neutral ligands to [Tl(C 6 F 5 ) 2 Cl]. The X-ray structure of complexes 3, 6 and 7 show thallium(III) centres in a tetrahedral, trigonal bipyramidal or octahedral arrangements, respectively.