91087-90-0Relevant articles and documents
Formation of Germanium-Nitrogen Double Bonds in Reactions of the Electron-rich Germylene Bisgermanium(II) with a Range of Diazo-compounds
Glidewell, Christopher,Lloyd, Douglas,Lumbard, Keith W.
, p. 501 - 508 (2007/10/02)
The electron-rich germylene Ge2 reacts with the diazo-compounds R1CH2COC(N2)R2 1 = H, R2 = CO(OEt), SO2C6H4Me-p, or COPh; R1, R2 = -CMe2CH2C(O)->, which contain an enolisable function, to yield the heterocycles ; the weakly acidic diazo-compounds ethyl diazoacetate and diazoacetophenone yield bis-adducts Ge2 (R = OEt or Ph).Diazo-compounds containing two non-enolisable substituents yield mono-adducts with Ge2 which can be hydrolysed to yield the diol Ge(OH)22 and, in one example, the corresponding hydrazone H2NN=C(COPh)CO(OEt).These adducts appear to be thermodinamically stable in an aprotic solvent, but can be trapped by addition of ethanol, to yield Ge2(OEt)2>, or of diazoacetophenone to yield Ge22>.All the reactions of the germylene with diazo-compounds can be rationalised in terms of the initial formation of a germyleneazine 2Ge=N-N=C(X)Y, which readily adds any available protic species to give a germane derivative.MNDO calculations on model systems are in accord with the experimental findings and also explain their differences from results previously obtained using the simpler germylene GePh2.
