TeX(4) (X = F, Cl, Br) as Lewis acids - complexes with soft thio- and seleno-ether ligands

TeF(4) reacts with OPR(3) (R = Me or Ph) in anhydrous CH(2)Cl(2) to give the colourless, square based pyramidal 1?:?1 complexes TeF(4)(OPR(3))] only, in which the OPR(3) is coordinated basally in the solid state, (R = Me: d(Te-O) = 2.122(2) ?; R = Ph: d(Te-O) = 2.1849(14) ?). Variable temperature (19)F{(1)H}, (31)P{(1)H} and (125)Te{(1)H} NMR spectroscopic studies strongly suggest this is the low temperature structure in solution, although the systems are dynamic. The much softer donor ligands SMe(2) and SeMe(2) show a lower affinity for TeF(4), although unstable, yellow products with spectroscopic features consistent with TeF(4)(EMe(2))] are obtained by the reaction of TeF(4) in neat SMe(2) or via reaction in CH(2)Cl(2) with SeMe(2). TeX(4) (X = F, Cl or Br) causes oxidation and halogenation of TeMe(2) to form X(2)TeMe(2). The Br(2)TeMe(2) hydrolyses in trace moisture to form BrMe(2)Te-O-TeMe(2)Br], the crystal structure of which has been determined. TeX(4) (X = Cl or Br) react with the selenoethers SeMe(2), MeSe(CH(2))(3)SeMe or o-C(6)H(4)(SeMe)(2) (X = Cl) in anhydrous CH(2)Cl(2) to give the distorted octahedral monomers trans-TeX(4)(SeMe(2))(2)], cis-TeX(4){MeSe(CH(2))(3)SeMe}] and cis-TeCl(4){o-C(6)H(4)(SeMe)(2)}], which have been characterised by IR, Raman and multinuclear NMR ((1)H, (77)Se{(1)H} and (125)Te{(1)H}) spectroscopy, and via X-ray structure determinations of representative examples. Tetrahydrothiophene (tht) can form both 1?:?1 and 1?:?2 Te?:?L complexes. For X = Br, the former has been shown to be a Br-bridged dimer, Br(3)(tht)Te(μ-Br)(2)TeBr(3)(tht)], by crystallography with the tht ligands anti, whereas the latter are trans-octahedral monomers. Like its selenoether analogue, MeS(CH(2))(3)SMe forms distorted octahedral cis-chelates, TeX(4){MeS(CH(2))(3)SMe}], whereas the more rigid o-C(6)H(4)(SMe)(2) unexpectedly forms a zig-zag chain polymer in the solid state, TeCl(4){o-C(6)H(4)(SMe)(2)}](n), in which the dithioether adopts an extremely unusual bridging mode. This is in contrast to the chelating monomer, cis-TeCl(4){o-C(6)H(4)(SeMe)(2)}], formed with the analogous selenoether and may be attributed to small differences in the ligand chelate bite angles. The wider bite angle xylyl-linked bidentates, o-C(6)H(4)(CH(2)EMe(2))(2) behave differently; the thioether forms cis-chelated TeX(4){o-C(6)H(4)(CH(2)SMe)(2)}] confirmed crystallographically, whereas the selenoether undergoes C-Se cleavage and rearrangement on treatment with TeX(4), forming the cyclic selenonium salts, C(9)H(11)Se](2)TeX(6)]. The tetrathiamacrocycle, 14]aneS(4) (1,4,8,11-tetrathiacyclotetradecane), does not react cleanly with TeCl(4), but forms the very poorly soluble TeCl(4)(14]aneS(4))](n), shown by crystallography to be a zig-zag polymer with exo-coordinated 14]aneS(4) units linked via alternate S atoms to a cis-TeCl(4) unit. Trends in the (125)Te{(1)H} NMR shifts for this series of Te(iv) halides chalcogenoether complexes are discussed.