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Phosphasilaallenes >Si=C=P- and phosphagermaallenes >Ge=C=P- review

Domenii publicaţii > Chimie + Tipuri publicaţii > Articol în revistã ştiinţificã

Autori: Jean Escudie, Gabriela Nemes

Editorial: Elsevier, Comptes Rendus Chimie, 2010.

Rezumat:

Phosphasilaallene Tip(Ph)Si = C = PMes* (Tip = 2,4,6-triisopropylphenyl, Mes* = 2,4,6-tri-tert-butylphenyl) and phosphagermaallene Mes2Ge = C = PMes* (Mes = 2,4,6-trimethylphenyl) have been obtained by dehalogenation of their corresponding dihalophosphametallapropenes > E(X)-C(X′) = P− by tert-butyllithium. They dimerize above −40 °C by a cycloaddition involving two E = C double bonds or the E = C and the P = C double bonds but can be characterized at low temperature by trapping reactions and by low field shifts in 31P, 29Si and particularly 13C NMR for the sp carbon atom. Owing to a small increase in the steric hindrance, phosphagermaallene Tip(t-Bu)Ge = C = PMes* can be stabilized and isolated. The Ge = C double bond undergoes nearly quantitative [2 + 1] cycloadditions with chalcogens and [2 + 2] cycloadditions with aldehydes or ketones. The surprisingly stable lithiochlorosilane R(Cl2)Si-C(Li) = PMes* (R = 9-methylfluorenyl) behaves as a synthetic equivalent of the phosphasilaallene R(Cl)Si = C = PMes*. With two alkyl groups (t-Bu) on the germanium atom, the phosphagermaallene t-Bu2Ge = C = PMes* is not obtained but its formal dimers 1,3-digermacyclobutanes have been isolated.

Cuvinte cheie: phosphagermaallenes // Phosphasilaallenes