Bismuth amides

Bismuth is an important element in many of the new high-temperature, oxide superconductors and in a variety of heterogeneous mixed oxide catalysts. Some of the methods employed in the preparation of these materials, namely sol-gel and chemical vapor deposition processes, require bismuth alkoxides as precursors and a number of papers on these compounds have recently been published.1 One synthetic route to bismuth alkoxides, which avoids the more commonly used trihalide starting materials and the often troublesome separation of alkali metal halides, involves the reaction between a bismuth amide and an alcohol according to the following equation ... 

Since relatively little has been published on the synthesis and properties of homoleptic bismuth amides,2,3 details on the preparation of two such compounds, Bi(NMe2)3 and Bi N(SiMe3)2 3, are described herein. 

Bis(2-methyl-1,8-naphthyridine)tetracarbonyldirhodium(I) perchlorate, 3827 Bis(2-methylpyridine)sodium, 3518 Bismuth amide oxide, 0229 Bismuth, 0226... 

THF, a mild exothermic reaction took place with the disappearance of the yellow colour of the bismuth amide. After removal of THF in a rotatory evaporator, the remaining slurry was triturated with petroleum ether to give bismuth tris(lV-phenyl-A, lV -dimethylureide) (2.92 g, 87%) [75JINC(37)2011]. 

JCS(D)1649] treatment of bismuth amides with alcohols or thiols gives the corresponding substituted products and secondary amines. 

The most common procedure for preparing bismuth alkoxides is the substitution reaction of bismuth halides with alkali metal alkoxides. The alternative is treatment of bismuth amides with alcohols. Bismuth alkoxides such as trimethoxide, triethoxide and triisopropoxide were first prepared in 80-93% yields by the reaction between BiCl3 and alkali metal alkoxides by Mehrotra et al. in 1966. Bismuth alkoxides are less soluble in organic solvents and the yields after purification by sublimation are generally very low (10-20%) [66IJC537]. Known aliphatic alkoxides include Bi(OEt)3... 

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