Halobismuthine complex salts and related compounds

HMPA (0.058 g, 0.325 mmol) was added dropwise to a stirred solution of bromodiphenylbis-muthine (0.072 g, 0.172 mmol) in THF (5 ml) at room temperature. This was followed by the addition of a solution of AgBp4 (0.032 g, 0.162 mmol) in THF (5 ml), which led to the formation of a pale yellow precipitate that turned dark grey after a few minutes. The mixture was filtered through a Celite bed and the colorless filtrate was concentrated under vacuum to about 5 ml. Hexane (20 ml) was added as an overlayer, and solvent diffusion over a period of days at -20°C afforded diphenylbismuth tetrafluoroborate-HMPA complex as colorless crystals (70%) [93JOM(460)C22]. 

An equimolar amount of bromodiphenylbismuthine and tetraphenylarsonium bromide were dissolved in boiling acetone. By gradually evaporating the solution, the arsonium salt separated out as pale yellow needles, m.p. 179-182°C [69JOM(20)99]. 

Treatment of a bismuth trihalide with electron-rich arenes affords arene-BiX3 TT-complexes. When the reaction is carried out in the presence of AICI3, the corresponding cationic ir-complexes are formed [87AG(E)74]. The arenes employed so far are benzene, toluene, mesitylene, hexamethyl-benzene, perylene, pyrene, acenaphthene, phenanthrene, fluorene, and fluor-anthene-p-xylene (1/0.5). The isolated compounds are summarized in Table 2.29. 

A suspension of bismuth chloride (0.25 g, 0.79 mmol) in mesitylene (25 ml) was heated to 60°C and then filtered. A colorless filtrate was obtained, from which BiCl3 l,3,5-Me3QH3 precipitated out as colorless plates (0.3 g, 87%), m.p. 157°C (decomp.) [86AG(E)757]. 

Compound R Synthetic Yield (%) M.p.(°C) method Physical data Reference 

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