Four- five- and six-co-ordinated pentafluorophenylthallium(III) complexes.: Crystal structures of [Tl(C6F5)3(OPPh3)], [Tl(C6F5)2Cl(OPPh3)]2 and [Tl(C6F5)2(OdppmO)2][Tl(C6F5)2Cl2]

[NBu4][Ag(C6F5)(2)] or [Ag(C6F5)] act as arylating ligands able to transfer two or one pentafluorophenyl groups to [Tl(C6F5)(2)Cl] leading to [NBu4][Tl(C6F5)(4)] (1) and [Tl(C6F5)(3)(diox)] (diox = 1,4 dioxane) (2) in an improved synthesis, the latter being a starting material for the synthesis of [Tl(C6F5)(3)(OPPh3)] (3) and [Tl(C6F5)(3)(PPh3)] (4). However, [Ag(C6F5)L] does not transfer the pentafluorophenyl group when reacted with [Tl(C6F5)(2)Cl] and the complexes [Tl(C6F5)(2)Cl(py)](2) (5), [Tl(C6F5)(2)Cl(OPPh3)](2) (6) and [Tl(C6F5)(2)(OdppmO)(2)][Tl(C6F5)(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(C6F5)(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. (C) 2002 Elsevier Science B.V. All rights reserved.