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′-dimethylpropylene 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) Å, 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) Å, α = 103.55(1), β = 93.710(8), γ = 95.98(1)°, D_calc = 1.664 Mg/m³, R = 0.090.