Bismuth ether complexes, preparation

Crown ether complexes of bismuth nitrate were prepared by reacting Bi(N03)3 5H20 in 3 1 MeCN MeOH with a stoichiometric amount of the crown ether (101). Bi(N03)3(12-croum-4) has bismuth in a 10-coordinate Cs 4A,6B-expanded dodecahedral geometry 31, in which all four ether oxygen atoms are bound to the bismuth center... 

Bismuth tribromide may be prepared by dissolving Bi O in excess concentrated hydrobromic acid. The slurry formed is allowed to dry in air, then gendy heated in a stream of nitrogen to remove water, and finally distilled in a stream of dry nitrogen. Bismuth tribromide is soluble in aqueous solutions of KCl, HCl, KBr, and KI but is decomposed by water to form bismuth oxybromide [7787-57-7] BiOBr. It is soluble in acetone and ether, and practically insoluble in alcohol. It forms complexes with NH and dissolves in hydrobromic acid from which dihydrogen bismuth pentabromide tetrahydrate [66214-38-8] H2BiBr 4H2O, maybe crystallized at —lO C. 

Organoboron complexes of the MR BR3 andMBR4 MAlR4 types merit attention from the safety standpoint. Numerous metal alkyls can be prepared by electrolysis of these compounds (Table 11). It is recommended that the dimethyl ether of diethylene glycol should be used as solvent. A small amount of water is added to increase the electrical conductivity of the solution [110]. Electrolysis of tetraalkylboron complexes in aqueous solution with a soluble anode has also been described [58]. In this last case alkyl derivatives of mercury, bismuth, and lead are obtained. Tin and antimony anodes become passivated, and the yields of the respective organometallic compounds are small. 

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