Tris bismuthane

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)... 

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]. 

Bu3Bi mediates the allylation of carbonyl compounds with allyl bromide to give a mixture of homoallyl alcohols and fheir allyl ethers (Scheme 14.133) [278], Tris(4-methoxyphenyl)bismuthane catalyzes the cyanation of carbonyl compounds with MesSiCN [175], In the presence of fluoride ions (CeFsjsBi undergoes nucleophilic substitution with an activated C-F bond of perfluorinated compounds to transfer three CgFj groups [279]. (CFsjsBi can also act as a trifluoromethyl anion equivalent [280]. 

A variety of substituted W arylpiperidines (110) were obtained by arylation of 4-oxopiperidines (109) with various tris(3-substituted phenyl)bismuthane and copper diacetate. 10 ... 

Modest to moderately good yields of the alkylated amines were obtained upon treatment with the symmetrical trialkylbismuth derivatives. With primary amines, trimethylbismuthane led preferentially to the disubstituted product, but tris(2-phenylethyl)bismuthane afforded only the product of monosubstitution. 

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