Pentacoordinate silicon complexes with dynamic motion resembling a pendulum on the SN2 reaction pathway

Muhammad Sohail, R. Panisch, A. Bowden, A. R. Bassindale, P. G. Taylor, A. A. Korlyukov, D. E. Arkhipov, L. Male, S. Callear, S. J. Coles, M. B. Hursthouse, R. W. Harrington, W. Clegg

Research output: Contribution to journalArticle

30 Citations (Scopus)

Abstract

A series of glutarimide derivatives which has two carbonyl coordination sites for intramolecular pentacoordination at silicon with a X 1+nSiC3-nO moiety have been synthesised and characterized. The substituent (leaving group) effects on the Si-O bond exchange between the two coordination sites (resembling a pendulum) have been studied by comparison of the differently substituted (X = F, Cl, OTf, Br and I) structures. The activation parameters for the Si-O bond exchange process were measured by NMR and separately computed and are consistent with the strength of Si-O bond coordination and the nature of the leaving group, X. The temperature-dependent 29Si NMR spectroscopy is supported by X-ray crystallography and shows that the tetrahedral reactant is converted into pentacoordinate intermediates by intramolecular O-Si association followed by reversion to a tetrahedral geometry by Si-X dissociation. The two association/dissociation patterns offer a model for nucleophilic substitution at a silicon atom. A continuum of structures on the SN2 reaction profile from the glutarimide derivatives correlates reasonably well with the structural data obtained from derivatives of lactams, diketopiperazines and quinolones. This journal is

Original languageEnglish
Pages (from-to)10971-10981
Number of pages11
JournalDalton Transactions
Volume42
Issue number30
DOIs
Publication statusPublished - 14 Aug 2013
Externally publishedYes

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Silicon
Pendulums
Diketopiperazines
Derivatives
Lactams
X Ray Crystallography
Quinolones
Association reactions
Magnetic Resonance Spectroscopy
X ray crystallography
Nuclear magnetic resonance spectroscopy
Temperature
Ion exchange
Substitution reactions
Chemical activation
Nuclear magnetic resonance
Atoms
Geometry
glutarimide

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Sohail, M., Panisch, R., Bowden, A., Bassindale, A. R., Taylor, P. G., Korlyukov, A. A., ... Clegg, W. (2013). Pentacoordinate silicon complexes with dynamic motion resembling a pendulum on the SN2 reaction pathway. Dalton Transactions, 42(30), 10971-10981. https://doi.org/10.1039/c3dt50613d

Pentacoordinate silicon complexes with dynamic motion resembling a pendulum on the SN2 reaction pathway. / Sohail, Muhammad; Panisch, R.; Bowden, A.; Bassindale, A. R.; Taylor, P. G.; Korlyukov, A. A.; Arkhipov, D. E.; Male, L.; Callear, S.; Coles, S. J.; Hursthouse, M. B.; Harrington, R. W.; Clegg, W.

In: Dalton Transactions, Vol. 42, No. 30, 14.08.2013, p. 10971-10981.

Research output: Contribution to journalArticle

Sohail, M, Panisch, R, Bowden, A, Bassindale, AR, Taylor, PG, Korlyukov, AA, Arkhipov, DE, Male, L, Callear, S, Coles, SJ, Hursthouse, MB, Harrington, RW & Clegg, W 2013, 'Pentacoordinate silicon complexes with dynamic motion resembling a pendulum on the SN2 reaction pathway', Dalton Transactions, vol. 42, no. 30, pp. 10971-10981. https://doi.org/10.1039/c3dt50613d
Sohail, Muhammad ; Panisch, R. ; Bowden, A. ; Bassindale, A. R. ; Taylor, P. G. ; Korlyukov, A. A. ; Arkhipov, D. E. ; Male, L. ; Callear, S. ; Coles, S. J. ; Hursthouse, M. B. ; Harrington, R. W. ; Clegg, W. / Pentacoordinate silicon complexes with dynamic motion resembling a pendulum on the SN2 reaction pathway. In: Dalton Transactions. 2013 ; Vol. 42, No. 30. pp. 10971-10981.
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