Coordination Complexes of Thallium (III) Chloride

Abstract

X-ray crystal structures are reported for two coordination complexes of thallium(III) chloride. In the neutral, monomeric complex [TlCl3(dmpu)2] (dmpu = N,N′-dimethyl-propylene urea), the coordination geometry around the thallium centre is essentially trigonal bipyramidal with equatorial chlorines and axial dmpu ligands similar to a number of other bis-ligand complexes previously characterised; crystal data, orthorhombic, space group Fdd2, a = 17.632(2), b = 27.257(3), c = 8.0353(9) A, D calc = 1.951 Mg/m3, R = 0.028. With the chelating ligand dppmO2 (Ph2P(O)CH2P(O)Ph2), the ionic compound [TlCl2(dppmO2)2] [TlCl4] · 2thf is obtained, which comprises an octahedrally coordinated thallium cation with trans chlorines and a tetrahedral [TlCl4]− anion; crystal data, triclinic, space group P 1, a = 10.7067(9), b = 16.190(2), c = 19.114(2) A, α = 103.55(1), β = 93.710(8), γ = 95.98(1)°, D calc = 1.664 Mg/m3, R = 0.090.