Bismuth lower halides

Some of the more important trends are shown by the oxides, which change from acidic for phosphorus to basic for bismuth, and by the halides, which have increasingly ionic character PC13 is instantly hydrolyzed by water to HPO(OH)2, and the other trihalides give initially clear solutions that hydrolyze to As203, SbOCl, and BiOCl, respectively. There is also an increase in the stability of the lower... 

The first attempts (5) to reduce metal salts with sodium at low temperatures were made by researchers working with solutions of sodium in liquid ammonia. In 1925 Kraus and Kurtz (7) showed that liquid ammonia solutions of sodium could be used to reduce halides of metals that form alloys with sodium. Operating at temperatures below the boiling point of the ammonia solutions they succeeded in reducing the halides of mercury, cadmium, zinc, tin, lead, antimony, bismuth, and thallium, and, by using an excess of sodium, concomitantly produced sodium alloys of these metals. Kraus and Kurtz postulated mechanisms for the reactions and showed that many of the alloys formed were unstable in liquid ammonia— i.e., they disproportionated into free sodium and lower sodium alloys. 

We have found that the main group metal and metalloid reductants mocury, bismuth, and antimony are highly effective " in reducing WCIe or M0CI5 at surprisingly lower temperatures than commonly used in the solid-state synthesis of early transition metal cluster halides. BorosUicate ampules can be substituted for the more expensive and less easily sealed quartz ampules at these lower temperatures, and the metals and metalloids are not as impacted by oxide coatings that inhibit sohd-state reactions with more active metals. These lower temperatures may allow access to kinetic products, such as trinuclear clusters, instead of thermodynamic products. 

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