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The tetravalent SeCl4 and SeBr4 are reduced in the presence of thioether ligands L (SMe2, tht) or L–L (MeS(CH2)nSMe (n = 2 or 3), o-C6H4(SMe)2) in MeCN solution at 0 °C, forming Se(II) thioether complexes, including the crystallographically characterised halo-bridged chain polymers [SeX2(SMe2)] (X = Cl or Br), molecular trans-[SeX2(tht)2], cis-[SeBr2{MeS(CH2)2SMe}] and the thioether-bridged polymer [SeBr2{MeS(CH2)3SMe}], as the main products, together with halogenated ligand. The [SeX2(L)2] and [SeX2(L–L)] complexes are all based upon distorted square planar coordination, with two Se-based lone pairs assumed to occupy the (vacant) axial sites, and Se–S bond distances of ca. 2.4–2.6 Å. The 1:1 species [SeX2(SMe2)] are T-shaped with trans X groups and weak intermolecular SeX contacts. The SeCl2-thioether complexes are less stable than the bromides, both in solution in CH2Cl2 and as solids at ambient temperature. Reaction of SeBr4 with o-C6H4(SMe2)2 leads to the red complex cis-[SeBr2{κ1-o-C6H4(SMe)2}2] as the major product; together with a minor (yellow) product formed via bromination of the aromatic ring, [SeBr2{4-Br-1,2-(SMe)2-C6H3}2]. The crystal structure confirms a V-shaped SeBr2 unit with long (weak) κ1-interactions to one S donor (meta to the Br) from two brominated ligands – an extremely rare coordination mode for an o-phenylene dithioether. Similar reaction of o-C6H4(SMe2)2 with SeCl4 leads to several species, including monosulfonium cation, [1]+ formed by coupling of one thioether group to the C4-position of the phenylene backbone in an adjacent molecule, confirmed crystallographically. Carbon-sulfur coupling is also evident in the reaction of SeX4 with o-C6H4(CH2SMe)2, leading to two related cyclic sulfonium species, [2]+ and [3]+, which were structurally characterised as [SeBr4]2− and [Se2Cl6]2− salts respectively. Reaction of SeX4 with SeMe2 leads to halogenation of the ligand to form Me2SeX2 and reduction of the SeX4 to elemental selenium.
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