Metal bismuth halides

But first the synthesis had to come John was interested in reduced metal halides, particularly for the post-transition metals cadmium, galHum, and bismuth (his Ph.D. dissertation was on anhydrous aluminum halides and mixed halide intermediates, a good start for what was to come ). However, he was not yet actively interested in rare-earth metals and their remarkable solubility in their halides. But these elements lured him one floor below where Adrian Daane headed the metallurgy section of Spedding s empire. He knew how to produce rare-earth metals with high purity and in sufficient quantity and also how to handle tantalum containers. What if one gave it a tr/ and reduced some rare-earth metal halides (John insists that this term is used correctly) from their respective metals at high temperatures under appropriate conditions. 

A number of other metallic halide salts have been found to condense with ethylene oxide, propylene oxide, or epichlorohydrin in a similar fashion (Eq. 662). Among them are phosphorus trichloride/ 7- a 17 bismuth trichloride,1SM arsenic trichloride,1000 silicon tetrachloride/7 1 titanium tetrachloride/ 09 16,7 beryllium chlorido/189 and Won trifluoride.401 Depending on their reactivity, on the reactant ratio, and... 

Bismuth is an important element in many of the new high-temperature, oxide superconductors and in a variety of heterogeneous mixed oxide catalysts. Some of the methods employed in the preparation of these materials, namely sol-gel and chemical vapor deposition processes, require bismuth alkoxides as precursors and a number of papers on these compounds have recently been published.1 One synthetic route to bismuth alkoxides, which avoids the more commonly used trihalide starting materials and the often troublesome separation of alkali metal halides, involves the reaction between a bismuth amide and an alcohol according to the following equation ... 

Metal Halides. Reacts explosively or violently with the following calcium bromide iron(III) bromide or chloride iron(II) bromide or iodide cobalt(II) chloride silver fluoride all four mercury(II) halides copper(I) chloride, bromide or iodide copper(II) chloride and bromide ammonium tetrachlorocuprate zinc and cadmium chlorides, bromides, and iodides aluminum fluoride, chloride, and bromide thallium bromide tin(II) or (IV) chloride tin(IV) iodide arsenic trichloride and triiodide antimony and bismuth trichlorides, tribromides, and triiodides vanadium(V) chloride chromium(IV) chloride manganese(II) and iron(II) chlorides and nickel chloride, bromide, and iodide.17,22"25... 

Reaction of organoantimony and -bismuth anionic species with metal halides... 

On the basis of an inert pair of s electrons, formation of anionic species from anti-mony(III) and bismuth(lll) halides and their related mono- and di-organo derivatives follows if a halide ion is considered to approach the central atom trans to one of the bonds already present and the X /M—X system is treated via a three centre-four electron approach. This reproduces not only the observed structures of the anions but also the observed range of metal-halogen distances. An alternative, qualitative, molecular orbital approach is that a second halogen is bonded via the antibonding orbital of an M—X bond already present. 

From alkyl halides and bismuth metal (method F)... 

Activated bismuth metal reacts with alkyl halides or trifluoromethyl iodide in the presence or absence of metallic copper at high temperatures to afford a mixture of mono- and dihalobismuthines [61JINC213, 63AJC636, 97JA724]. 

Mixed bismuth-metal oxychlorides with or without added alkali or alkaline earth cations show low to moderate catalytic performance in the dehydroha-logenation of f rf-butyl halides [93BCJ347]. A Bi-Pd (Bi/Pd = 0.4-0.6) binary system supported on metal oxides is found to be an efficient catalyst for the dehydrohalogenation of 1,1,2-trichlorotrifluoroethane (FC-113) to trifluoroethene, a key intermediate to FC-134a, with 80-90% selectivity at 80-100% conversion [91CL841] (Scheme 5.23). 

A similar reaction consists of decomposition of the double salt of a diphenyl-halonium salt and a heavy-metal halide by a powdered metal (Reutow). It can be used for synthesis of aryl derivatives of a wide variety of metals such as mercury, tin, antimony, and bismuth.23... 

Samarium selenides. Reductive cleavage of ArSeSeAr by samarium is catalyzed by a great number of metal halides bismuth(III) chloride, cadmium chloride, chromium(IIl) chloride, cobalt(II) chloride, potassium iodide, and titanium(lV) chloride. The resulting samarium arylselenides readily react with various organic halides. 

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