H. Ernest Henderson

The Reactivity of Silicon and Germanium Carbodiimides with Protic Species

Abstract Silicon and germanium carbodiimides readily undergo protolytic cleavage with trihaloethanols to give, high yields of the ethers Me3MOCH2CX3 (M=Si,Ge; X=F,Cl). Similar reactions with selected thiols and selenols only occur with the germanium species to provide efficient syntheses of Me3GeSC2H5 and H3GeSeR (R=CH3, C6H5). The comparative reactions of weakly acidic Group IV or V species are not synthetically viable. Redistribution at nitrogen is noted from the identification of R3SiNCNGeR3 species (R3=Me3, Me2H) in mixtures of the symmetrical carbodiimides.

A high yield synthesis of some germanium-group VI species

The use of thiols as reactants with organotin oxygen compounds is a recognized preparative route to the corresponding organotin sulfur derivatives, l but similar reactions do not occur with silicon. Recently, 2 we described the preparation of a number of chalcogermanes via the cleavage of germanium carbodiimides with protic species. Although the Ge-N bond is very susceptible to nucleophilic attack, l i t t l e is known concerning the corresponding germoxy species. We find that the Ge-O bond is readily cleaved by the heavier chalcogenols in an analogous manner to the carbodiimideso This leads to compounds of the type (MenH3_nGe)2E and Me n H3_nGeER (E=S,Se; R=Me,Et; n_=O-3). The formation of the chalcogermanes is accompanied by quantitative yields of water.

The vibrational spectra of germane and silane derivatives—XI. Vibrational spectra and normal co-ordinate analyses of some thiogermanes

Abstract The i.r. and Raman spectra of the thiogermanes, (CH3)nH3-n, GeSCH3(n = 0–3) are reported and the fundamentals assigned. A normal co-ordinate analysis based on a modified valence force field supports the a priori assignments for all of the fundamental frequencies except the torsional modes.