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.