Bismuthane

Dentritic phenylene-bridged Bi bismuthanes were obtained from Ph2BiCl and />-Li2C6H4 and related reagents.144... 

Nucleophilic fluorine-aryl substitution in iodine pentafluoride with tetrakis(pentafluoro-phcnyl)silane or tris(pentafluorophenyl)bismuthane produces high-purity (pentafluorophen-yl)iodine tetrafluoride in good yield.133,134... 

When treated with iodine pentafluoride, triphenylbismuthane gives triphenylbismuth difluoride but no evidence for the formation of bismuth(V) derivatives was found in the reactions with tris(4-fluorophenyl)bismuthane and tris(trifluoromethyl)bismuthane. Fluorine-aryl (or alkyl) exchange takes place in these cases instead of oxidative fluorination.139140... 

Bismuthane Tris-[3(or 4)-fluoro-phcnyl]- XIII/8. 593 (Ar - MgX i BiClj)... 

The Rh-catalyzed reaction of triphenylbismuthane with a,/3-unsaturated carbonyl compounds in aqueous media under air gives the corresponding conjugated addition products (/3-phenyl carbonyl compounds) in moderate to good yields (Equation (72)). Dimethyl(phenyl)bismuthane also transfers the phenyl group exclusively. In the... 

When treated with a mixture of Ph3Bi and /-BuOOH in CCI4 or toluene, dibenzyl is oxidized to benzil (Equation (100)). The active oxidant is assumed to be an 02-eoordinated bismuthane complex (Ph3Bi-02).169 Triphenylmethane and 1,1-diphenylethane are oxidized by this complex to the corresponding hydroperoxides. 

Nowadays this important compound can be easily prepared on a scale up to 200 g when an emulsion of white phosphorus in 1,2-dimethoxyethane is treated vrith liquid sodium-potassium alloy and excess chlorotrimethylsilane is added to the suspension of the hitherto scarcely characterized Zintl phases Na3P and K3P, respectively. With decreasing yield the tris(trimethylsilyl) derivatives of arsane [3], stibane [4], and bismuthane [5] have also been obtained in the same way (Eq. 1). Meanwhile, hesitation to handle dangerous sodium-potassium alloy or white phosphorus led to the development of similar methods to prepare the phosphane [6,7]. 

Thermochromism of organometallic derivatives containing As, Sb or Bi 453 TABLE 10. Colours of seleno- and telluro-stibanes and bismuthanes... 

Resin-bound bismuthanes (81a-c) have also been prepared and used as a multidirectional linker for these C—N bond-forming reactions (Figure 20)337. The yields were approximately 30% lower than those reported for similar reactions in solution phase. 

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