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The first chalcogenoether complexes of Te(IV) chloride and bromide are prepared by reaction of the thioether with a suspension of TeX4 in anhydrous CH2Cl2, and the products characterised by IR, Raman, 1H and 125Te{1H} NMR spectroscopy and microanalysis. The structures of the distorted octahedral chelate complexes [TeX4{RS(CH2)2SR}] (X = Cl or Br; R = Me or iPr) and the centrosymmetric halo-bridged dimers [{X3(Me2S)Te}2(μ-X)2] (X = Cl or Br) involving Te(IV) are reported and the structures interpreted in terms of a three-centre-four-electron bonding model, with weak, secondary Te–S interactions. The structure of a unique Te(II) thioether complex, [TeCl{iPrS(CH2)2SiPr}][Te2Cl9] obtained as a decomposition product from a sample of [TeCl4{iPrS(CH2)2SiPr}], in which a Te(II) thioether cation and Te(IV) chloride anion are weakly associated viaμ2- and μ3-bridging Cl ligands, is also described. In this case distortions in the coordination environment at the Te(II) ion are attributed to the effects of the Te-based lone pairs.

Graphical abstract: Preparation and structures of tellurium(iv) halide complexes with thioether coordination

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