Atranes

The conformational energy of the 1-methylsilatrane molecule for sp³ and sp³d hybridization of the silicon atom was calculated. The known data on the structure of the atrane portion of the molecule are in good agreement with the results of the calculation for sp³d hybridization and differ radically from the results of the calculation for sp³ hybridization of the silicon atom. The conformational factors constitute a considerable contribution (11.4 kcal/mole) to the forced change in the hybridization of the silicon atom. An analysis of the dependence of the energy of the 1-methylsilatrane molecule on the distance between the Si and N atoms shows that a stable exo form, isolated to any extent by a considerable conformational barrier from the real structure with an SiN transannular interaction, does not exist.See [1] for communication XXXIV.Translated from Khimiya Geterotsiklicheskikh Soedinenii. No. 5, pp. 613–617, May, 1974.     

Reaction of α-and β-(trialkylsilyl)acroleins with a grignard reagent

Conclusions Reaction of- and-(trialkylsilyl)acroleins with methylmagnesium iodide forms the corresponding secondary unsaturated organosilicon alcohols. The reactions of-(trialkylsilyl)acroleins are accompanied by cleavage of the Si -C bond. The byproducts from -(trialkylsilyl)aeroleins are primary unsaturated alcohols and, -unsaturated organosilicon ketones.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 431–433, February, 1978.     

Determination of electron affinity of carbonyl radicals by means of negative ion mass spectrometry

Appearance energies of [M-H](-) ions from carbonyl compounds R-CO-R' (R,R' = H, CH(3), NH(2), OH) have been measured by means of negative ion mass spectrometry in resonant electron capture mode. Values of electron affinity of the corresponding radicals, CH(2)&dbond;C(X)O, NH&dbond;C(X)O and O&dbond;C(X)O, have been determined. Copyright 1999 John Wiley & Sons, Ltd.