Preparation of monomeric neutral or anionic tris(polyfluorophenyl)thallium(III) and of anionic heteronuclear tris(polyfluorophenyl)thallium–metal carbonyl complexes

Abstract

The complex [TlR₃(diox)](diox = 1,4-dioxan) has been prepared by the reaction of TlCl₃ with LiR (R = 2,4,6-C₆F₃H₂), or of [NBu₄][TlR₄] with HBF₄(R = C₆F₅) and subsequent addition of dioxan. The displacement of dioxan by (a) neutral ligands leads to [TlR₃L](L = OPPh₃, pyridine, PPh₃, or Ph₂PCH₂PPh₂); (b) anionic ligands affords Q[TlR₃X]{Q =[NBu₄]⁺ or [N(PPh₃)₂]⁺; X = Cl^–, CN^–, NO₃^–, or CF₃CO₂^–}; and (c) metal carbonylate gives Q[TlR₃M*]{M*=[Mo(cp)(CO)₃]^–(cp =η–C₅H₅), [W(cp)(CO)₃]^–, [Co(CO)₄]^– or [Mn(CO)₅]^–}.