Donor-stabilized silyl cations. 9. Two dissociation patterns of hexacoordinate silicon complexes: A model nucleophilic substitution at pentacoordinate silicon

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 inOrganometallics Vol. 24; no. 12; pp. 2913 - 2920
Main Authors Gostevskii, B, Silbert, G, Adear, K, Sivaramakrishna, A, Stalke, D, Deuerlein, S, Kocher, N, Voronkov, MG, Kalikhman, Kost, D
Format Journal Article
LanguageEnglish
Published WASHINGTON Amer Chemical Soc 06.06.2005
Subjects
Chemistry
Chemistry, Inorganic & Nuclear
Chemistry, Organic
Physical Sciences
Science & Technology
REARRANGEMENT
STEREODYNAMICS
INTRAMOLECULAR BASE STABILIZATION
TEMPERATURE
IONIC DISSOCIATION
EQUILIBRIUM
NEUTRAL HEXACOORDINATE
LIGAND
BOND
SALTS
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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 Si-29 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