Bismuthides

The existence of bismuthine was first demonstrated by using a radioactive tracer, Bi (8). Acid treatment of a magnesium plate coated with Bi resulted in the hberation of a volatile radioactive compound. In subsequent experiments, magnesium bismuthide [12048-46-3], Mg Bi, was treated with acid the yield, however, was only one part of bismuthine for every 20,000 parts of bismuth dissolved. Attempts to prepare bismuthine by reduction of bismuth trichloride with a borohydride have not been particularly successful. Experimental quantities ate best prepared by disproportionation of either methylbismuthine [66172-95-0], CH Bi, or dimethylbismuthine [14381-45-4], C2H. Bi (7) ... 

Bismuthides. Many intermetaUic compounds of bismuth with alkafl metals and alkaline earth metals have the expected formulas M Bi and M Bi, respectively. These compounds ate not saltlike but have high coordination numbers, interatomic distances similar to those found in metals, and metallic electrical conductivities. They dissolve to some extent in molten salts (eg, NaCl—Nal) to form solutions that have been interpreted from cryoscopic data as containing some Bi . Both the alkafl and alkaline earth metals form another series of alloylike bismuth compounds that become superconducting at low temperatures (Table 1). The MBi compounds are particularly noteworthy as having extremely short bond distances between the alkafl metal atoms. 

All three carboa—bismuth boads of trihen zylhismuthine [99715-52-3], C2 H2 Bi, (64) and triphenylbismuthine (65) can be cleaved by alkafl metals. Under some conditions, however, tertiary bismuthines react with sodium or potassium to yield secondary bismuthides. Thus a number of sodium dialkylbismuthides have been obtained by the iateraction of a trialkylbismuthine and sodium ia Hquid ammonia (66—69) ... 

The secondary bismuthides discussed herein are useful for preparing several types of organobismuth compounds, eg, tertiary bismuthines and dibismuthines. 

A number of compounds of the types RBiY2 or R2BiY, where Y is an anionic group other than halogen, have been prepared by the reaction of a dihalo- or halobismuthine with a lithium, sodium, potassium, ammonium, silver, or lead alkoxide (120,121), amide (122,123), a2ide (124,125), carboxylate (121,126), cyanide (125,127), dithiocarbamate (128,129), mercaptide (130,131), nitrate (108), phenoxide (120), selenocyanate (125), silanolate (132), thiocyanate (125,127), or xanthate (133). Dialkyl- and diaryUialobismuthines can also be readily converted to secondary bismuthides by treatment with an alkali metal (50,105,134) ... 

As the solid state structures of heterocyclic group 13 amides, phosphides and arsenides have been reviewed in the past,76 they will not be discussed here. Instead, the solid state structures of group 13 stibides and bismuthides will be described in detail. 

In contrast, the synthesis of monomeric stibides and bismuthides R2MER2 failed until we recently introduced an alternative, generally applicable pathway for the synthesis of monomeric group 13/15 compounds. We found that heterocycles may generally serve as starting compounds for the generation of their monomeric forms. In accordance with their formulation as head-to-tail adducts , strong Lewis bases are able to cleave the... 

Lithium amide, 15 129, 137 Lithium antimonide, 3 58 Lithium batteries, 15 135-136, 611 Lithium-bearing minerals, 15 122 Lithium bentonite, 6 696 Lithium benzoate, 3 635 15 137 Lithium bismuthide, alloy-like... 

Arsenides, antimonides and bismuthides. A number of salt-like related binary compounds formed with these semi-metals pertain to the following structure types NaCl, NiAs, ZnS, Na3As, FeS2, etc. 

Individually indexed alloys or intermetallic compounds are Aluminium amalgam, 0051 Aluminium-copper-zinc alloy, 0050 Aluminium-lanthanum-nickel alloy, 0080 Aluminium-lithium alloy, 0052 Aluminium-magnesium alloy, 0053 Aluminium-nickel alloys, 0055 Aluminium-titanium alloys, 0056 Copper-zinc alloys, 4268 Ferromanganese, 4389 Ferrotitanium, 4391 Lanthanum-nickel alloy, 4678 Lead-tin alloys, 4883 Lead-zirconium alloys, 4884 Lithium-magnesium alloy, 4681 Lithium-tin alloys, 4682 Plutonium bismuthide, 0231 Potassium antimonide, 4673 Potassium-sodium alloy, 4646 Silicon-zirconium alloys, 4910... 

No, the editor didn t know what this name meant either.) It means salts of the triva-lent anions of Group V, restricted in [1] to arsenides, antimonides and bismuthides and prepared by reaction of sodium pnictides with anhydrous halides of transition and lanthanide metals. This violently exothermic reaction may initiate as low as 25°C. Avoidance of hydrated halides is cautioned since these are likely to react uncontrollably on mixing. Another paper includes a similar reaction of phosphides, initiated by grinding [2], Nitrides are reported made from the thermally initiated reaction of sodium azide with metal halides, a very large sealed ampoule is counselled to contain the nitrogen [3],... 

Fig. 12 Molecular structures of functionalized antimonide (a-d) and bismuthide (e-j) cages.

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