Synthesis of arylthallium complexes using organomercury compounds. Crystal and molecular structures of [NMe4][Tl(C6H4NNPh-2)Cl3] and [Tl(C6H4CH2-NMe2-2)Cl2]

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Abstract
The reaction of [Hg(C6H4NNPh-2)2] or [Hg(C6H4CH2NMe2-2)2] with [NMe4]2[TlCl5](1:2) affords [NMe4][Tl(C6H4NNPh-2)Cl2] or [NMe4][Tl(C6H4CH2NMe2-2)Cl3] respectively. These two anionic complexes react with NaClO4 to give the neutral compounds [Tl(C6H4NNPh-2)Cl2] and [Tl(C6H4CH2NMe2-2)Cl2]. The crystal structure of [NMe4][Tl(C6H4NNPh-2)Cl3] shows a distorted trigonal bipyramidal geometry around the thallium atom, if the rather weak interaction between thallium and the farther N atom [2.786(8)Å] is included. The nitrogen and carbon atoms occupy axial and equatorial sites, respectively, and a five-membered TlC2N2 ring is observed. The Tl–Cl distances are normal, with Tl–Clax[2.575(3)Å] longer than Tl–Cleq[2.500(4) and 2.427(3)Å]. The crystal structure of [Tl(C6H4CH2NMe2-2)Cl2] consists of a dimer with two asymmetric chlorine bridges [Tl–Cl 2.530(4) and 2.937(3)Å]. The chelating ligand again gives rise to a five-membered ring, here TlC3N. Each thallium atom has a distorted trigonal bipyramidal environment in which the axial positions are occupied by the nitrogen atom of the aryl ligand [Tl–N 2.513(8)Å] and the weakly bonded bridging chlorine. The equatorial sites are occupied by the carbon atom of the aryl ligand [Tl–C 2.127(10)Å], the other bridging chlorine, and a terminal chlorine [Tl–Cl 2.392(3)Å].

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