ISSN:
1572-9001
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
Abstract MNDO calculations have been carried out on the reactions of the electron-rich germylene L2Ge [L=(H3Si)2N] with diazo compounds, as models for the experimentally observed reactions of L2Ge [L=(Me3Si)2N]. The most stable form of the 1∶1 adduct of L2Ge with N2C(COOMe)2 is found to have a cyclic configuration resulting from a strong intramolecular interaction between the oxygen of one of the carbonyl groups and the germanium atom. Protonation of this cyclic adduct occurs at nitrogen, giving an intermediate, addition to which of nucleophiles X− provides acyclic L2Ge(X)NHN(COOMe)2, as observed experimentally. Two similar cyclic adducts are formed between L2Ge and N2C(COCH3)(COOCH3), the most stable of which provides, after a proton shift, the observed 1,3,4,2-oxadiazagermine system $$L_2 $$ . Adduct formation between Me2Si=NSiMe3 and simple Lewis bases (H2O, NH3, THF, H2CO) is calculated to be strong, but the corresponding adducts of Me2Ge=NSiMe3 are very weak: much stronger adducts are predicted for L2GeNNC(COOMe)2.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF00674256
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