Indium halides reaction with halogens

Treatment of tethered alkyne-allyl halides with indium metal in halogenated solvents affords carbocyclic vinyl halides via a novel atom-transfer reaction. The reactions are operationally facile and proceed smoothly at room temperature even with sub-stoichiometric quantities of indium. Use of a halogenated solvent containing a different... 

Specialized methods include (a) reaction of halogens with Rsin to yield R InX3 compounds, and (b) reaction of an indium(I) or indium(II) halide with an organic halide via... 

A number of reactivity studies have been performed on 6 and 8 and indicate a strongly polar (if not ionic) Mn—E bond Mn "—E,+ (E = In, Tl). Thus heterolytic bond dissociation occurs in polar ligating solvents such as MeCN or DMF, and halogens, hydrogen halides, and alkyl halides readily add across the metal-metal bond in a manner consistent with the polarity described above (13,13a,18). In the thallium example, however, the reactions are generally more complicated and result in T1(I) salts [e.g., Eq. (3)], and metal exchange reactions are also more facile, e.g., the synthesis of 6 from 8 and indium metal. In general, therefore, the chemistry of 6 and 8 is consistent with predominantly ionic behavior. 

Crystalline indium trihalides are readily prepared from the reaction of the metal and halogen (sometimes in the presence of solvent), from metal-I-HX, or by the electrochemical oxidation of the metal in a non-aqueous solution of X2. Indium trichloride and tribromide have indium octahedrally coordinated by halide in the solid state, whereas the triiodide exists as the dimer I2lnl2lnl2 in the solid or in solution all three halides are dimeric in the vapor phase. The many adducts of these compounds with neutral donors have been extensively reviewed previously. ... 

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