The University of Southampton
University of Southampton Institutional Repository

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

Pentacoordinate silicon complexes with dynamic motion resembling a pendulum on the SN2 reaction pathway
Pentacoordinate silicon complexes with dynamic motion resembling a pendulum on the SN2 reaction pathway
A series of glutarimide derivatives which has two carbonyl coordination sites for intramolecular pentacoordination at silicon with a X1+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 Si-29 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 S(N)2 reaction profile from the glutarimide derivatives correlates reasonably well with the structural data obtained from derivatives of lactams, diketopiperazines and quinolones.
0300-9246
10971-10981
Sohail, M.
6191a551-7b8c-4e1d-983d-5aac36058e59
Panisch, R.
c0f6c71b-e05d-478f-a9bc-b02cd3345c88
Bowden, A.
1d2f089f-2390-46a6-8954-42ad669a42fd
Bassindale, A.R.
61ee8519-38e5-4880-a127-9cdec50fb2e4
Taylor, P.G.
35352cdd-207c-4dc9-934c-8bffd8c5160a
Korlyukov, A.A.
306b9846-8d68-4ea0-9afa-b5de87fea729
Arkhipov, D.E.
47f46cd9-1632-4f43-9632-f2b515596daf
Male, L.
975dd2b7-a080-4319-bfb6-e74f51e62f2f
Callear, S.
2c981465-2ca6-4acd-a628-3f850990d47e
Coles, S.J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Hursthouse, M.B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Harrington, R.W.
e912893d-1846-4f66-8f20-b810e7aef239
Clegg, W.
a29c8e43-b6a6-4db7-9ce2-e44da8792cb5
Sohail, M.
6191a551-7b8c-4e1d-983d-5aac36058e59
Panisch, R.
c0f6c71b-e05d-478f-a9bc-b02cd3345c88
Bowden, A.
1d2f089f-2390-46a6-8954-42ad669a42fd
Bassindale, A.R.
61ee8519-38e5-4880-a127-9cdec50fb2e4
Taylor, P.G.
35352cdd-207c-4dc9-934c-8bffd8c5160a
Korlyukov, A.A.
306b9846-8d68-4ea0-9afa-b5de87fea729
Arkhipov, D.E.
47f46cd9-1632-4f43-9632-f2b515596daf
Male, L.
975dd2b7-a080-4319-bfb6-e74f51e62f2f
Callear, S.
2c981465-2ca6-4acd-a628-3f850990d47e
Coles, S.J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Hursthouse, M.B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Harrington, R.W.
e912893d-1846-4f66-8f20-b810e7aef239
Clegg, W.
a29c8e43-b6a6-4db7-9ce2-e44da8792cb5

Sohail, M., 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. and Clegg, W. (2013) Pentacoordinate silicon complexes with dynamic motion resembling a pendulum on the SN2 reaction pathway. Dalton Transactions, 42 (30), 10971-10981. (doi:10.1039/c3dt50613d).

Record type: Article

Abstract

A series of glutarimide derivatives which has two carbonyl coordination sites for intramolecular pentacoordination at silicon with a X1+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 Si-29 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 S(N)2 reaction profile from the glutarimide derivatives correlates reasonably well with the structural data obtained from derivatives of lactams, diketopiperazines and quinolones.

Full text not available from this repository.

More information

e-pub ahead of print date: 22 May 2013
Published date: 2013
Organisations: Organic Chemistry: Synthesis, Catalysis and Flow, Chemistry

Identifiers

Local EPrints ID: 362492
URI: http://eprints.soton.ac.uk/id/eprint/362492
ISSN: 0300-9246
PURE UUID: 20601846-f72c-4985-b21d-bb4efcc93708
ORCID for S.J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

Catalogue record

Date deposited: 25 Feb 2014 14:00
Last modified: 18 Feb 2021 16:53

Export record

Altmetrics

Contributors

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

University divisions

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of http://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×