Synthesis, characterisation and structures of thio-, seleno- and telluro-ether complexes of indium(III) halides

Gurnani, Chitra, Jura, Marek, Levason, William, Ratnani, Raju, Reid, Gillian and Webster, Michael (2009) Synthesis, characterisation and structures of thio-, seleno- and telluro-ether complexes of indium(III) halides. Dalton Transactions, 9, 1611-1619. (doi:10.1039/b816148h).

Abstract

The indium(III) halo-bridged octahedral dimers [InX2(L–L)(-X)2InX2(L–L)] (X = Cl: L–L = MeS(CH2)2SMe, MeSe(CH2)2SeMe, nBuSe(CH2)2SenBu), the ionic trans-[InX2(L–L)2][InX4] (X = Cl: L–L = iPrS(CH2)2SiPr; X = Br: L–L = MeS(CH2)2SMe, iPrS(CH2)2SiPr, MeSe(CH2)2SeMe), cis-[InCl2(thiamacrocycle)][InCl4] (thiamacrocycle = [12]aneS4 or [14]aneS4) and the neutral, octahedral [InCl3([9]aneS3)] and [InCl3{MeC(CH2SMe)3}] were obtained in good yield by the reaction of 1:1 molar ratios of InX3 with the ligand in anhydrous CH2Cl2 solution. The distorted tetrahedral [InX3(Me2Se)] (X = Cl, Br or I) and [InX3(Me2Te)] (X = Br or I) were obtained from 1:3 and 1:2 molar ratios respectively of InX3 and Me2E (E = Se or Te) also in CH2Cl2. The ligand-bridged, distorted tetrahedral dimers [(InCl3)2{2-o-C6H4(CH2SMe)2}] and [(InCl3)2{2-MeTe(CH2)3TeMe}] are formed even from a 1:1 In:ligand ratio. Key structure types were confirmed from crystal structures of [InCl2{RSe(CH2)2SeR}(-Cl)2InCl2{RSe(CH2)2SeR2}] (R = Me or nBu), trans-[InX2{iPrS(CH2)2SiPr}2][InX4] (X = Cl or Br), trans-[InBr2{MeSe(CH2)2SeMe}2][InBr4], cis-[InCl2([14]aneS4)][InCl4] and [InBr3(Me2Se)]. The bulk complexes have been characterised by IR and Raman spectroscopy and microanalyses, while 1H, 77Se{1H} and 125Te{1H} NMR spectroscopy show that the compounds are extremely labile in solution and undergo rapid dynamic exchange equilibria. Comparisons are drawn between these structurally rather diverse In(III) chalcogenoether complexes and the corresponding Ga(III) species (all of which are neutral and involve distorted tetrahedral coordination). The reaction of TlCl3 with Me2E (E = Se or Te) shows that chlorination of Me2E rather than adduct formation occurs, while no reaction occurred between TlCl3 and Me2S, consistent with Tl(III) being a very poor Lewis acid.

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Contributors

Author: William Levason

Author: Gillian Reid

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