Co-ordination compounds of indium. Part 47. Indium(I) and thallium(I) derivatives of alkanedithiols

Abstract

The electrochemical oxidation of anodic indium in non-aqueous solutions of a series of alkanedithiols R(SH)₂(R = 1,2-C₂H₄, 1,2-C₃H₆, 1,3-C₃H₆, 1,4-C₄H₈, 2,3-C₄H₈, 1,5-C₅H₁₀, or 1,6-C₆H₁₂) gives the unusual indium(I) compounds In[SR(SH)], containing the alkanethiol(thiolato) ligand. These compounds can be deprotonated by either NEt₃ or NBuⁿ₄OH to form salts of the [In^I(S₂R)]^– anion; this anionic complex can be oxidized by I₂ to the corresponding indium(III) species [In^IIII₂(S₂R)]^–, which can also be produced by successive I₂ oxidation and deprotonation of In^I[SR(SH)]. Reaction with the o-quinones o-X₄C₆O₂ gives the catecholato derivatives [In^III{SR(SH)}(O₂C₆X₄-o)](X = Cl or Br). Carbon disulphide insertion occurs at only one In–S bond. With thallium, the products of electrochemical oxidation are Tl₂(S₂R) in all the cases studied.