Radical anions of hypervalent silicon compounds: 1-substituted silatranes

The first representatives of the radical anions of silatranes XSi(OCH2CH2)3N – organic derivatives of the pentacoordinate silicon atom (X = Ph, 1; p-NO2PhO, 2a; m-NO2PhO, 2b; o-NO2PhO, 2c) – were obtained and characterized by EPR spectroscopy. The structure of 1(−˙), 2a(−˙), 2b(−˙), and 2c(−˙) in po...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2015-05, Vol.17 (19), p.12735-12746
Main Authors: Belogolova, Elena F, Vakul'skaya, Tamara I, Sidorkin, Valery F
Format: Article
Language:English
Subjects:
Anions
Astronomical models
Atomic beam spectroscopy
Cations
Constants
Radicals
Silicon
Silicon compounds
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Summary:The first representatives of the radical anions of silatranes XSi(OCH2CH2)3N – organic derivatives of the pentacoordinate silicon atom (X = Ph, 1; p-NO2PhO, 2a; m-NO2PhO, 2b; o-NO2PhO, 2c) – were obtained and characterized by EPR spectroscopy. The structure of 1(−˙), 2a(−˙), 2b(−˙), and 2c(−˙) in polar solvents (C-PCM and COSMO models) was studied at the UMP2 and UB3PW91 levels of theory. The variation of structural characteristics and pentacoordinate character of the silicon atom in 1, 2 upon the attachment of an additional electron to them is discussed. The experimental hyperfine coupling constants aN, aH and those calculated with the UTPSSh/IGLOIII and UB3LYP/N07D methods using the UB3PW91 geometry (taking into account an effect of the potassium cation in the case of 1(−˙)) are in good mutual agreement.
ISSN:1463-9076
1463-9084
DOI:10.1039/c4cp06046f