Bismuth

Abstract

Symmetrical tertiary bismuthines are parpared by:

• 1. Reacting bismuth trichloride with organometallic compounds, such as Grignard compounds, trialkylauminum, tetraalkyllead, organosodium, and crganolithium derivatives.

• 2. Decomposition of aryldiazonium chloride-bismuth trichloride double salts in ethyl acetate or in acetone with bismuth powder or in absolute ethanol with copper bronze, followed by reduction of triarylbismuthine dichloride which may be formed by hydrazine hydrate.

• 3. Decomposition of diaryl-chloronium, bromonium, or iodonium fluoroborates or chlorobismutates with bismuth powder in acetone.

• 4. Reacting bismuth trichloride with potassium aryldiazocarboxylates in acetone in the presence of bismuth powder.

• 5. Arylation of metallic bismuth with aryldiazonium fluoroborates in acetone.

• 6. Arylation of bismuth trichloride with arylhydrazines in hydrochloric acid in the presence of copper(II) and iron(III) chlorides.

• 7. Reduction of tertiary bismuthine dihalides, R₃BiX₂, with hydrazine hydrate in alcohol, or with mercury(II) chloride in ethanol, or with mercury oxide in alkaline solution, or with lithium aluminum hydride or lithium tetrahydroborate at very low temperatures.

• 8. Disproportionation diorganohalobismuthines in the presence of mercury(II) chloride in ethanol or with mercury oxide in alkaline solution.

• 9. Reaction of diarylbimuthine-alkali metal derivatives, R₂BiM, with aryl halides in liquid ammonia.

• 10. Metathetic reactions of triarylbismuthines with alkyllithium or alkylsodium compounds to form trialkylbismuthines.

• 11. Metathetic reaction of bismuth trichloride with cyanotrimethylsilane to form probably tricyanobismuthine.

• 12. Electrolysis of silver cyanide in pyridine, using a bismuth anode, to form tricyanobismuthine.