Four- five- and six-co-ordinated pentafluorophenylthallium(III) complexes.: Crystal structures of [Tl(C 6F 5) 3(OPPh 3)], [Tl(C 6F 5) 2Cl(OPPh 3)] 2 and [Tl(C 6F 5) 2(OdppmO) 2][Tl(C 6F 5) 2Cl 2

Abstract

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