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- W2050909133 abstract "The dimethylgermyldimethylsilylmethanediiron octacarbonyl Me2GeCH2Si(Me2)Fe2(CO))8 (1) is obtained from the cyclization of dimethylgermyldimethylsilylmethane with Fe(CO)5 under UV irradiation. Various CO substitution reactions with phosphines and GeFe or GeSi cleavage reactions are described. The reactions with organic carbonyl compounds result in the formation of new silylated and germylated heterocycles. The reactions with oxygen and sulfur probably involve, by decomposition of unstable thia- or oxa-germasiletanes, [Me2GeX] (X = O, S) and [Me2SiCH2] intermediates and give the heterocycles Me2SiCH2Ge(Me2)XGe(Me2)X and Me2SiCH2Ge(Me2)CH2SiMe2X. This mechanism is supported by the pyrolysis of the 2,2,6,6,4,4,8,8-octamethyl-2,6-digerma-4,8-disila-1,5-dithiocane (dimer of the germasilathietane Me2GeCH2Si(Me2)S) which affords the same heterocycles. Le diméthylgermyldiméthylsilylméthane di-fer octacarbonyle (1) a été obtenu par réaction de cyclisation du diméthylgermyl diméthylsilylméthane avec Fe(CO)5 sous irradiation ultraviolette. 1 est un dérivé très réactif. On observe des réactions de substitution de CO, des réactions de clivage des liaisons GeFe et SiFe, par divers dérivés halogénés. Les réactions de 1 avec les dérivés carbonyles organiques conduisent par réaction d'insertion—élimination à de nouveaux hétérocycles silagermaniés. Dans les réactions de sulfuration (S8) ou d'oxydation (O2) de 1 la formation de thia ou oxagermasilétannes est postulée. Leur décomposition avec formation d'intermédiaires insaturés germathione ou germanone (X = S ou O) et silaéthylène conduit aux hétérocycles Me2SiCH2Ge(Me2)XGe(Me2)X et Me2SiCH2Ge(Me2)CH2Si(Me2)X. Ce mécanisme est confirmé par la pyrolyse de l'octaméthyl-2,2,4,4,6,6,8,8 digerma-2,6 disila-4,8 dithiocanne-1,5 (dimère du germasilathiétanne Me2GeCH2Si(Me2)S), synthétisé par ailleurs, qui s'accompagne de la formation des mêmes hétérocycles." @default.
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- W2050909133 date "1990-04-01" @default.
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- W2050909133 title "Complexe hétérocyclique tétranucléaire: le diméthylgermyl diméthylsilylméthane di-fer octacarbonyle" @default.
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- W2050909133 doi "https://doi.org/10.1016/0022-328x(90)87300-3" @default.
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