(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.

Journal Article | Published | English

No fulltext has been uploaded

Author
; ; ; ; ;
Abstract
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.
Publishing Year
ISSN
eISSN
PUB-ID

Cite this

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.
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.
This data publication is cited in the following publications:
This publication cites the following data publications:

62 References

Data provided by Europe PubMed Central.


Ruoff, J. Chem. Phys. 96(), 1992

AUTHOR UNKNOWN, 0

Huntley, J. Chem. Soc. Dalton Trans. 6(), 1980

Murata, Acta Crystallogr. 20(), 1966

Hinchley, Dalton Trans. (), 2004

AUTHOR UNKNOWN, 0

Ross, 1992

Sipachev, J. Mol. Struct. 121(), 1985

Sipachev, 1999

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

Biegler-König, J. Comput. Chem. 22(), 2001

Export

0 Marked Publications

Open Data PUB

Web of Science

View record in Web of Science®

Sources

PMID: 15991212
PubMed | Europe PMC

Search this title in

Google Scholar