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Indium reacts with both Ph,S, and Ph,Se, in refluxing toluene to give the compounds In(EPh), (E = S or Se) in high yield. Under similar conditions tin gives Sn( EPh),. Thallium reacts with Ph,Se, t o form TI(SePh), but does not react with Ph, S, . Neither zinc nor gallium reacts with Ph,S, or Ph,Se,. With mixtures of Ph, E, and I , , indium yields the previously unreported In1 (EPh), compounds. The reactions of In(SePh), are those of a typical indium(iii) Lewis acid. Possible factors affecting the reactions of metals with Ph,S, or Ph,Se, are briefly discussed.

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The electrochemical oxidation of anodic indium in non-aqueous solutions of a series of C&i q, ) gives the unusual indium(i) compounds In[SR(SH)], containing the alkanethiol(thio1ato) ligand. These compounds can be deprotonated by either NEt, or NBun40H to form salts of the [Inl(S,R)] -anion; this anionic complex can be oxidized b y I, to the corresponding indium(iii) species [Inllll,(S,R)] -, which can also be produced by successive I , oxidation and deprotonation of In ' [SR(SH)]. Reaction with the o-quinones 0-X4C60, gives the catecholato derivatives [In~11{SR(SH)}(0,C6X4-o)] (X = CI or Br). Carbon disulphide insertion occurs at only one In-S bond. With thallium, the products of electrochemical oxidation are TI,(S,R) in all the cases studied.

, 804 (1987) In(SPh), is readily prepared by the reaction of InCl, and NaSPh in methanol. The compound is a Lewis acid, forming 1:1 adducts with 2,2'-bipyridine, 1, 10-phenanthroline, N, N, N', N'-tetramethylethanediamine, bis(diphenylphosphino)ethane, and dimethylsulphoxide, and 1:2 adducts with pyridine, trimethylamine, and triphenylphosphine. Reaction with R4NX (X = C1, Br, I) or similar salts gives R4N[XIn(SPh)3] salts, which are 1:l electrolytes. The structure of Ph4P[BrIn(SPh),] has been determined by X-ray methods: The crystals are monoclinic, space group P2,/c, with cell dimensions a = 9.964 (3) [Traduit par la revue]

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. TUCK. Can. J. Chem. 67, 746 (1989).The electrochemical oxidation of anodic indium in acetonitrile solutions of the aromatic diols R(OH)2 (= 1,2-dihydroxybenzene; 2,3-dihydroxynaphthalene; 2,2'-dihydroxybiphenyl; 1,2-dihydroxytetrabromobenzene) yields the new compounds In[OR(OH)]. These unusual indium(1) species can be oxidized by iodine to I~"'I~[oR(oH)], and by the ortho-quinone Br4C602 to I~"'[oR(oH)](o~c~B~~). The hydroxy-0x0 ligand can be deprotonated by Et3N to give the salts Et3NH[In(02R)]. The nature of these reactions, and the structure of the initial products, are confirmed by infrared and 'H nmr spectroscopy.