(Dimethylaminomethyl)trifluorosilane, Me2NCH2SiF3 - A model for the alpha-effect in aminomethylsilanes

Mitzel NW, Vojinovic K, Foerster T, Robertson HE, Borisenko KB, Rankin DWH (2005)
CHEMISTRY-A EUROPEAN JOURNAL 11(17): 5114-5125.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
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Abstract / Bemerkung
F3SiCH2NMe2 was prepared as a model for the investigation of the nature of the alpha-effect in alpha-aminosilanes, by fluorination Of Cl3SiCH2NMe2 with SbF3. Under less mild conditions Si-C bond cleavage was also observed, leading to the double adduct F,Si(Me2NCH2SiF3)(2), which was characterised by a crystal structure analysis showing that the central SiF4 unit is connected to Me2NCH2SiF3 via (SiN)-N-... dative bonds and (FSi)-Si-... contacts. F3SiCH2NMe2 was characterised by multinuclear NMR spectroscopy (H-1, C-13, N-15, F-19 and Si-29), gas-phase IR spectroscopy and mass spectrometry. It is a dimer in the crystal (X-ray diffraction, crystal grown in situ), held together by two Si-N dative bonds. In solution and in the gas phase the compound is monomeric. The structure of the free molecule, determined by gas-phase electron diffraction, showed that, in contrast to former postulates, there are no attractive Si-N interactions. Ab initio calculations have been carried out to explain the nature of the bonding. F3SiCH2NMe2 has an extremely flat bending potential for the Si-C-N angle; the high degree of charge transfer from the Si to the N atoms which occurs upon closing the Si-C-N angle is in the opposite direction to that expected for a dative bond. The topology of the electron density of F3SiCH2NMe2 was analysed. Solvent simulation calculations have shown virtually no structural dependence on the medium surrounding the molecule. The earlier postulate of Si -> N dative bonds in SiCN systems is discussed critically in light of the new results.
Stichworte
silicon; alpha-effect; amines; electron diffraction; noncovalent interactions
Erscheinungsjahr
2005
Zeitschriftentitel
CHEMISTRY-A EUROPEAN JOURNAL
Band
11
Ausgabe
17
Seite(n)
5114-5125
ISSN
0947-6539
eISSN
1521-3765
Page URI
https://pub.uni-bielefeld.de/record/1928595

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Mitzel NW, Vojinovic K, Foerster T, Robertson HE, Borisenko KB, Rankin DWH. (Dimethylaminomethyl)trifluorosilane, Me2NCH2SiF3 - A model for the alpha-effect in aminomethylsilanes. CHEMISTRY-A EUROPEAN JOURNAL. 2005;11(17):5114-5125.
Mitzel, N. W., Vojinovic, K., Foerster, T., Robertson, H. E., Borisenko, K. B., & Rankin, D. W. H. (2005). (Dimethylaminomethyl)trifluorosilane, Me2NCH2SiF3 - A model for the alpha-effect in aminomethylsilanes. CHEMISTRY-A EUROPEAN JOURNAL, 11(17), 5114-5125. doi:10.1002/chem.200500359
Mitzel, N. W., Vojinovic, K., Foerster, T., Robertson, H. E., Borisenko, K. B., and Rankin, D. W. H. (2005). (Dimethylaminomethyl)trifluorosilane, Me2NCH2SiF3 - A model for the alpha-effect in aminomethylsilanes. CHEMISTRY-A EUROPEAN JOURNAL 11, 5114-5125.
Mitzel, N.W., et al., 2005. (Dimethylaminomethyl)trifluorosilane, Me2NCH2SiF3 - A model for the alpha-effect in aminomethylsilanes. CHEMISTRY-A EUROPEAN JOURNAL, 11(17), p 5114-5125.
N.W. Mitzel, et al., “(Dimethylaminomethyl)trifluorosilane, Me2NCH2SiF3 - A model for the alpha-effect in aminomethylsilanes”, CHEMISTRY-A EUROPEAN JOURNAL, vol. 11, 2005, pp. 5114-5125.
Mitzel, N.W., Vojinovic, K., Foerster, T., Robertson, H.E., Borisenko, K.B., Rankin, D.W.H.: (Dimethylaminomethyl)trifluorosilane, Me2NCH2SiF3 - A model for the alpha-effect in aminomethylsilanes. CHEMISTRY-A EUROPEAN JOURNAL. 11, 5114-5125 (2005).
Mitzel, Norbert W., Vojinovic, K, Foerster, T, Robertson, HE, Borisenko, KB, and Rankin, DWH. “(Dimethylaminomethyl)trifluorosilane, Me2NCH2SiF3 - A model for the alpha-effect in aminomethylsilanes”. CHEMISTRY-A EUROPEAN JOURNAL 11.17 (2005): 5114-5125.

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