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Donor-stabilized silyl cations. 9. Two dissociation patterns of hexacoordinate silicon complexes: A model nucleophilic substitution at pentacoordinate silicon
B. Gostevskii, G. Silbert, K. Adear, , D. Stalke, S. Deuerlein, N. Kocher, M.G. Voronkov, I. Kalikhman, D. Kost
Published in
Volume: 24
Issue: 12
Pages: 2913 - 2920
Hexacoordinate silicon bischelates with bulky monodentate alkyl ligands tend to ionize, while those with electron-withdrawing CF3 substituents on the chelate rings resist ionization. A hexacoordinate silicon complex with both of these structural features was prepared and was found, by its temperature-dependent 29Si NMR spectroscopy, to undergo a reversible neutral dissociation of the N→Si dative bond, which satisfies both tendencies. The results are supported by crystallographic structure analyses and by nonempirical MO calculations of isodesmic reaction energies. © 2005 American Chemical Society.
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