Monogermylated ketenes, R(Et3Ge)CCO, have been prepared by the Wolff rearrangement of carbenoids, Et3GeC̈COR, generated by the copper-catalyzed decomposition of the corresponding α-(triethylgermyl)diazo ketones in hexane. In contrast, triethylsilyldiazoacetone decomposes over copper by another reaction scheme to give, unexpectedly 1,1-diethyl-3,5-dimethyl-2-oxa-1-sila-3-cyclopentene. The copper-catalyzed interaction of Et3MC(N2)COOEt (M = Si, Ge, Sn) with bis(triethylsilyl)- or bis(triethylgermyl)-mercury results in high yield of the corresponding bimetalated ketenes, Et3M(Et3M′)CCO, where M and M′ are Si, Ge or Sn. The first step in this interaction probably involves the insertion of the carbenoid, Et3MC̈CO2Et, into the Group IV element-mercury bond. The general procedure for the preparation of α-metalated diazocarbonyl compounds via readily available bis(triethylsilyl)- and bis(triethylgermyl)-mercury is described.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry
- Materials Chemistry