Indium trihalides

In contrast to the non-trivial routes for the syntheses of pure aluminum(I) or gallium(I) subhalides, indium(I) chloride or bromide can simply be prepared by melting mixtures of elemental indium and indium trihalides [39]. When these in-dium(I) halides were treated with bulky alkyllithium compounds, deep violet orga-noelement indium dusters (13-18) were obtained [Eq. (3)] [40, 41]. 

Similar reactions occur with other halogens. Monohalides of indium include chloride, bromide and iodide. Monohalides are obtained by passing indium trihalides over heated indium ... 

The imide [(MeInNC6F5)4] 5" was synthesized by a similar method. The tetrameric cubanes [In4X4(p-NBu )4] (where X Cl, Br or I) formed from the corresponding indium trihalide, InXa and LiHNBu have In4N4 heterocubane structures that are similar to their aluminium and gallium counterparts. The chloride [In4Cl4(NBu )4] is shown in Figure 8.11. 

Crystalline indium trihalides are readily prepared from the reaction of the metal and halogen9 (sometimes in the presence of solvent), from metal+ HX, or by the electrochemical oxidation of the metal in a non-aqueous solution of X2.20 Indium trichloride and tribromide have indium octahedrally coordinated by halide in the solid state, whereas the triiodide exists as the dimer I2lnl2InI2 in the solid or in solution all three halides are dimeric in the vapor phase.9 The many adducts of these compounds with neutral donors have been extensively reviewed previously.5,7... 

The diphosphine-type ligands provide an opportunity for the complexation with group III and IV metals. For instance, the reaction of gallium or indium trihalides with l,2-bis-(diphenylphosphanyle)benzene (DP) leads to the formation of [(DP)2MC12]+[MX4] complexes. 

New studies by our group have shown that the indium trihalides InX3 (X = Cl, Br, I) also react with Na2[M2(CO)i0] according to (86) ... 

Only two methods for the preparation of phenylindium halides have been reported (i) transmetallation of Grignard reagents with indium trihalides [10] and (ii) the reaction of triphenylindium with Br2 or I2 [11]. No work had appeared in the literature concerning the direct preparation of diphenylindium halides from indium metal and aryl halides. The only related work reported was the preparation of pentafluorophenylindium compounds from indium... 

Reaction with Allylic Halides, Alcohols, and their Derivatives. Allylation of allyl and propargyl trimethylsilyl ethers as well as benzyl and propargylic alcohol derivatives proceeds in the presence of a catalytic amount of Lewis acids, such as ZnC, TMS(OTf), and B(C6F5)3. Direct substitutions of the hydroxyl group of allylic, ben-zylic, and propargylic alcohols are catalyzed by HN(S02F)2, a rhenium-oxo complex, and InCls (eq 27). A combination of chlorodimethylsilane and allyltrimethylsilane effectively promotes the deoxygenative allylation of aromatic ketones in the presence of a catalytic amount of an indium compound, such as indium trihalide or metallic indium (eq 28). Allylation of cyclic allylic acetates with allyltrimethylsilane can be catalyzed by molecular iodine. ... 

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