Chapter 53. Gas-Phase Reactions of Free Methyl Cations with Amines and Their Organosilicon Analogues: A Radiochemical Study

  1. Prof. Dr. Norbert Auner2 and
  2. Prof. Dr. Johann Weis3
  1. T. A. Kochina,
  2. D. V. Vrazhnov,
  3. E. N. Sinotova and
  4. B. F. Shchogolev

Published Online: 5 MAY 2008

DOI: 10.1002/9783527619924.ch53

Organosilicon Chemistry V: From Molecules to Materials

Organosilicon Chemistry V: From Molecules to Materials

How to Cite

Kochina, T. A., Vrazhnov, D. V., Sinotova, E. N. and Shchogolev, B. F. (2003) Gas-Phase Reactions of Free Methyl Cations with Amines and Their Organosilicon Analogues: A Radiochemical Study, in Organosilicon Chemistry V: From Molecules to Materials (eds N. Auner and J. Weis), Wiley-VCH Verlag GmbH, Weinheim, Germany. doi: 10.1002/9783527619924.ch53

Editor Information

  1. 2

    Department of Inorganic Chemistry, University of Frankfurt, Marie-Curie-Straße 11, 60439 Frankfurt am Main, Germany

  2. 3

    Consortium of Electrochemical Industry GmbH, Zielstattstraße 20, 81379 Munich, Germany

Author Information

  1. Institute for Silicate Chemistry of Russian Academy of Sciences ul. Odoevskogo 24/2, Saint Petersburg 199155, Russia Tel.: +7812 3284802 — Fax: +7812 3285401

Publication History

  1. Published Online: 5 MAY 2008
  2. Published Print: 26 SEP 2003

ISBN Information

Print ISBN: 9783527306701

Online ISBN: 9783527619924

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Keywords:

  • methyl cations;
  • amines;
  • ion-molecule reactions

Summary

Reactions of free methyl cations with diisobutylamine (1), isobutylaminotrimethylsilane (2) and hexamethyldisilazane (3) were studied by the radiochemical method. It was shown that in all cases studied, the proton transfer is a predominant channel. Probabilities for the reaction to enter this channel are: 0.87 for 1, 0.67 for 2 and 0.93 for 3. The last value contradicts the well-known dependence of the lowering of the proton affinity of amines upon the CH3/SiH3 ratio. However, quantum chemical calculations have shown that the interaction of the silazane HOMO with the CH3+ LUMO is symmetry forbidden. This fact may result in the lowering of the methyl cation affinity for silazanes and preference for the proton transfer channel.