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

Boris Gostevskii; Gilad Silbert; Keren Adear; Akella Sivaramakrishna; Dietmar Stalke; Stephan Deuerlein; Nikolaus Kocher; Mikhail G. Voronkov; Inna Kalikhman; Daniel Kost

doi:10.1021/om0500568

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

Boris Gostevskii, Gilad Silbert, Keren Adear, Akella Sivaramakrishna, Dietmar Stalke, Stephan Deuerlein, Nikolaus Kocher, Mikhail G. Voronkov, Inna Kalikhman, Daniel Kost

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

45 Scopus citations

Abstract

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.

Original language	English
Pages (from-to)	2913-2920
Number of pages	8
Journal	Organometallics
Volume	24
Issue number	12
DOIs	https://doi.org/10.1021/om0500568
State	Published - 6 Jun 2005

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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Gostevskii, B., Silbert, G., Adear, K., Sivaramakrishna, A., Stalke, D., Deuerlein, S., Kocher, N., Voronkov, M. G., Kalikhman, I., & Kost, D. (2005). Donor-stabilized silyl cations. 9. Two dissociation patterns of hexacoordinate silicon complexes: A model nucleophilic substitution at pentacoordinate silicon. Organometallics, 24(12), 2913-2920. https://doi.org/10.1021/om0500568

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abstract = "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.",

author = "Boris Gostevskii and Gilad Silbert and Keren Adear and Akella Sivaramakrishna and Dietmar Stalke and Stephan Deuerlein and Nikolaus Kocher and Voronkov, {Mikhail G.} and Inna Kalikhman and Daniel Kost",

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Gostevskii, B, Silbert, G, Adear, K, Sivaramakrishna, A, Stalke, D, Deuerlein, S, Kocher, N, Voronkov, MG, Kalikhman, I & Kost, D 2005, 'Donor-stabilized silyl cations. 9. Two dissociation patterns of hexacoordinate silicon complexes: A model nucleophilic substitution at pentacoordinate silicon', Organometallics, vol. 24, no. 12, pp. 2913-2920. https://doi.org/10.1021/om0500568

TY - JOUR

T1 - Donor-stabilized silyl cations. 9. Two dissociation patterns of hexacoordinate silicon complexes

T2 - A model nucleophilic substitution at pentacoordinate silicon

AU - Gostevskii, Boris

AU - Silbert, Gilad

AU - Adear, Keren

AU - Sivaramakrishna, Akella

AU - Stalke, Dietmar

AU - Deuerlein, Stephan

AU - Kocher, Nikolaus

AU - Voronkov, Mikhail G.

AU - Kalikhman, Inna

AU - Kost, Daniel

PY - 2005/6/6

Y1 - 2005/6/6

N2 - 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.

AB - 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.

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DO - 10.1021/om0500568

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VL - 24

SP - 2913

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JO - Organometallics

JF - Organometallics

IS - 12

ER -

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

Abstract

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