Organothallium compounds: XVII. Halogenobis(polyfluorophenyl)thallium(III) complexes

The preparations, stabilities and structures of the complexes R₂TlX and R₂ LTlX (R = C₆F₅, p-HC₆F₄, or o-HC₆F₄; X = Br or Cl; L = Ph₃PO, 2,2′-bipyridyl (bpy) or Ph₃P) have been examined or (R = C₆ F₅) reinvestigated. The derivatives R₂TlX are monomeric in acetone, from which the complex (p-HC₆F₄)₂ Me₂COTIBr has been isolated. In this solvent, the complexes R₂LTlX (L = Ph₃PO, bpy, or Ph₃P) undergo partial dissociation by loss of L. When L = bpy, there is also slight ionization into R₂LTl⁺ and R₂TlX⁻₂. The acceptor properties of R₂TlX compounds towards uncharged ligands decrease R = C₆F₅ ⋍ p-HC₆F₄ 〉 o-HC₆F₄ 〉 Ph. Dimeric behaviour is observed for R₂TIX compounds in benzene, whilst R₂LTlX (L = Ph₃PO or bpy) derivatives show slight but significant association. In the solid state, R₂TlX compounds are considered to be polymeric with five coordinate thallium, and R₂LTlX derivatives to be dimeric with five (L = Ph₃PO) or six (L = bpy) coordinate thallium by contrast with four coordinate dimeric and four or five coordinate monomeric structures previously proposed for the respective pentafluorophenyl derivatives. Halogen bridging is unsymmetrical for R = C₆F₅ or p-HC₆F₄, but may be more symmetrical for R = o-HC₆F₄ when L = Ph₃PO or bpy. Reported structural data for the complexes (C₆F₅)LTlX (L = Ph₃AsO, Ph₃P, Ph₃As, or 1,10-phenanthroline; X = Br or Cl) and (C₆F₅)₂TlCl⁻₂ are reinterpreted and the proposed structures revised.