Donor-Stabilized Silyl Cations. 9. Two Dissociation Patterns of Hexacoordinate Silicon Complexes:  A Model Nucleophilic Substitution at Pentacoordinate Silicon1

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 temperatur...

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Published in:Organometallics 2005-06, Vol.24 (12), p.2913-2920
Main Authors: Gostevskii, Boris, Silbert, Gilad, Adear, Keren, Sivaramakrishna, Akella, Stalke, Dietmar, Deuerlein, Stephan, Kocher, Nikolaus, Voronkov, Mikhail G, Kalikhman, Inna, Kost, Daniel
Format: Article
Language:eng ; jpn
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Summary: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.
ISSN:0276-7333
1520-6041
DOI:10.1021/om0500568