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 [InI(S2R)]– anion; this anionic complex can be oxidized by I2 to the corresponding indium(III) species [InIIII2(S2R)]–, which can also be produced by successive I2 oxidation and deprotonation of InI[SR(SH)]. Reaction with the o-quinones o-X4C6O2 gives the catecholato derivatives [InIII{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.