From triarylbismuth dihalides

In some limited solvent systems, a metathetical reaction between triphenyl-bismuth dichloride and silver perchlorate results in the formation of oxybis-(triphenylbismuth) diperchlorate [72JOM(36)323]. This type of compound is only obtained when a mixture of water-benzene is used as the reaction medium. When the same reaction is carried out in absolute ethanol or in pure acetone, tetraphenylbismuthonium perchlorate and acetonyltriphenylbismuthonium perchlorate are obtained as the respective product (Section 3.3.1). 

Oxybis(triphenylbismuth) dinitrate is also obtainable by treating an acetone solution of triphenylbismuth dichloride with an aqueous solution of silver nitrate. 

A benzene solution (25 ml) of triphenylbismuth dichloride (1.6 g, 3 mmol) and an aqueous solution (25 ml) of silver perchlorate (1.38 g, 5 mmol) were mixed together and stirred for 3 h at room temperature. The benzene layer was separated and the remaining mixture was filtered. The residue, which contained silver chloride and most of the oxybis(triphenylbismuth) diperchlorate, was treated with 95% ethanol (50 ml). The mixture was filtered and the filtrate was concentrated under vacuum. The compound was finally obtained as white crystals by adding diethyl ether slowly and cooling down to 5°C. Yield, 50%, m.p. 148°C (decomp.) [72JOM(36)323]. 

Triarylbismuth dihalides are converted to oxybis(triarylbismuth) dihalides by treatment with sodium hydroxide in alcoholic solutions [72JOM(36)323, 960M5613]. Treatment of triarylbismuth difluorides with hexamethyldisilox-ane in the presence of trimethylsilyl triflate gives oxybis(triarylbismuth) ditri-flates [94JCS(P 1)1739]. 

Synthesis of oxybis[tris(4-A, A -dimethylaminophenyl)bismuth] dichloride 

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From triarylbismuth dihalides and sulfonamides or amides (method... 

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