Indium complexes bromides

Barium iodate 1-hydrate, synthesis 4 Indium(I) bromide, synthesis 6 Hexachlorodisiloxane, synthesis 7 Trichlorosilanethiol, synthesis 8 Tris(acetylacetonato)silicon chloride, synthesis 9 Titanium(III)chloride, synthesis 11 Bis[tris(acetylacetonato)titanium(IV)] hexachloro-titanate(IV), synthesis 12 Zirconium(IV) iodide, synthesis 13 (Triphenyl) aminophosphonium chloride, synthesis 19 (Dimethylamido)phosphoryl dichloride, synthesis 20 Bis(dimethylamido)phosphoryl chloride, synthesis 21 Trimeric and tetrameric phosphonitrilic bromides, synthesis 23 Phosphorus(V) chloride-boron trichloride complex, synthesis 24... 

Although in this chapter we shall be restricting coverage to reactions of transition-metal complexes, the phenomenon of oxidative addition is not confined to this type of compound. Such reactions are also well established for non-transition metals—a recently reported example concerns the oxidative addition of methyl bromide to indium(i) bromide to give InBr2Me— and for non-metals, as in the reaction of phosphorus trichloride with chlorine, to cite a very familiar example. Likewise, reductive eliminations are known and studied outside the area of transition-metal complexes. One example has been mentioned in Chapter 1 of Part II of this volume, namely the elimination of alkyl halides from the thallium(iii) compounds TlRXa. ... 

Reaction with Propargyl Halides. The indium-mediated coupling of propargyl bromide with a variety of imines and imine oxides afforded homo-propargylamine derivatives in aqueous media under mild conditions.78 Propargylation of glyoxylic oxime ether in the presence of a catalytic amount of palladium(O) complex and indium(I) iodide in aqueous media was also studied (Eq.11.47).79... 

In order to increase the Lewis acidity of the indium centers in compounds such as 52, the preparation of derivatives that incorporate a tetrafluorophenylene backbone has also been pursued. l,2-Bis(halomercurio)tetrafluorobenzene (halide = chloride (53) or bromide (54)) reacts with two equivalents of the corresponding indium(I) halide in THF at 25 °C to afford the tetrakis(T i ) adduct of the respective 9,10-dihalo-9,10-dihydro-9,10-diinda-octafluoroanthracene (halide = chloride (55) or bromide (56)) (Scheme 22). Compound 56 is also prepared by the reaction of (o-C6F4Hg)3 (4) with InBr in refluxing toluene followed by treatment with THF. The formation of the diindacycles 55 and 56 in the reaction of 53 and 54 with two equivalents of the corresponding indium(I) halide is surprising since, in principle, bis(indiumdihalide) complexes would be the expected products. This cyclization... 

The indium-mediated reaction of cinnamyl bromide with 5-formyluracil derivatives gives the corresponding homoallylic alcohols (Equation (21)). The presence of G4 carbonyl is essential for high diasteroselection owing to the complexation with indium.182... 

Indium ate complexes (indates) bearing methyl and alkenyl groups have been prepared and both the tendency of emigration and regioselectivity toward cinnamyl bromide have been investigated (Scheme 120). The alkenyl group is... 

Methylisoxazole-5-carboxylic acid was converted into the corresponding 5-carboxamides and 5-(l/7-pyrazol-l-ylcarbonyl) derivatives in satisfactory yields by treatment with thionyl chloride and amines or pyrazoles <2002SC425>. A three-component assembly of isoxazole-5-carboxylic acid chloride, 1,1-dimethylallene, and bis-pinacolatodiboron, catalyzed by a phosphine-free palladium complex, gave 2-acylallylboronate derivatives regiose-lectively (Equation 47) <2003JA12576>. On the other hand, a mild procedure allowed the preparation of /3,7-unsaturated ketones by simple reaction of 3-aryl-5-methylisoxazole-4-carboxylic acid chlorides with allyl bromide and indium in DMF (Equation 48) <1997TL8745>. 

As bromide complexes, indium has been extracted with diethyl ether [68] or diisopropyl ether, and gold(III) (from 3 M HBr), also with di(2-chloroethyl) ether [69]. 

Among the methods for the separation of small amounts of indium before its determination, the solvent extraction methods in general, and extraction of indium-iodide and -bromide complexes in particular, are of the utmost importance. 

The indium iodide complex [1-3] is > 99% extracted into diethyl ether from 0.5-2.5 M HI (6-30%). Gallium is not extracted under these conditions, but it is extracted from 6 M HCl. The hydriodic acid can be replaced by 0.5-3 M H2SO4 containing 15-20% of Kl. Chloride, bromide, fluoride, phosphate, and citrate do not interfere in the extraction of In from iodide media. Under the optimum conditions for the extraction, Tl, Cd, and Sn (and some Bi, Zn, Hg, and Sb) are extracted. Aluminium and Fe(II), like Ga, are not extracted. The indium iodide complex has also been extracted into chloroform containing N-benzylaniline [4,5]. 

The indium bromide complex [6,7] can be extracted into diethyl ether from 4.5-5.5 M HBr (-40%). When extraction with DIPE is applied, the concentration of HBr should be -6 M. The selectivity of In extraction from a bromide medium is lower than that from iodide solutions. Ga, Fe(III), Sb(V), Au(III), Tl(III), Sn, and Mo are extracted with indium. Indium can be stripped with water from the ether extract. 

The bromide complex of indium gives extractable ion-associates with the xanthene basic dyes Rhodamine B [49] and triphenylmethane dyes. Brilliant Green [50,51], and Crystal Violet [52], extractable into non-polar solvents. The related dye. Malachite Green, has been used to form an associate with tetra-iodoindate, extractable with benzene, hexane, and CCI4 [53]. 

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