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Further studies of fluoride ion entrapment in octasilsesquioxane cages; X-ray crystal structure studies and factors that affect their formation

Further studies of fluoride ion entrapment in octasilsesquioxane cages; X-ray crystal structure studies and factors that affect their formation
Further studies of fluoride ion entrapment in octasilsesquioxane cages; X-ray crystal structure studies and factors that affect their formation
A range of fluoride-encapsulated octasilsesquioxane cage compounds have been prepared using the TBAF route. Our studies suggest that whilst it is relatively straightforward to prepare fluoride-encapsulated octasilsesquioxane cage compounds with adjacent sp(2) carbons, leading to a range of aryl and vinyl substituted compounds, the corresponding sp(3) carbon derivatives are more capricious, requiring an electron withdrawing group that can stabilize the cage whilst not acting as a leaving group. Analysis by X-ray crystallography and solution F-19/Si-29 NMR spectroscopy of R8T8@F- reveal very similar environments for the encapsulated fluoride octasilsesquioxane cages. Migration of a fluoride ion from inside the cage to outside the cage without breaking the T-8 framework and the possibility of encapsulating other anions within silsesquioxane cages have been also investigated.
0300-9246
2048-2059
Taylor, Peter G.
e59508fd-4cfb-422c-bbb0-b70cfb6aa195
Bassindale, Alan R.
285ee4e0-58d0-4178-a0d9-d7e0d1efbebd
El Aziz, Youssef
986fe8b4-3600-4439-b697-817a617d4fd8
Pourny, Manuel
a30afeb6-8a7e-4328-a9d6-a0547b2a2a69
Stevenson, Richard
66094368-4883-448f-a952-82936ab0fd48
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Taylor, Peter G.
e59508fd-4cfb-422c-bbb0-b70cfb6aa195
Bassindale, Alan R.
285ee4e0-58d0-4178-a0d9-d7e0d1efbebd
El Aziz, Youssef
986fe8b4-3600-4439-b697-817a617d4fd8
Pourny, Manuel
a30afeb6-8a7e-4328-a9d6-a0547b2a2a69
Stevenson, Richard
66094368-4883-448f-a952-82936ab0fd48
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8

Taylor, Peter G., Bassindale, Alan R., El Aziz, Youssef, Pourny, Manuel, Stevenson, Richard, Hursthouse, Michael B. and Coles, Simon J. (2012) Further studies of fluoride ion entrapment in octasilsesquioxane cages; X-ray crystal structure studies and factors that affect their formation. Dalton Transactions, 41 (7), 2048-2059. (doi:10.1039/c1dt11340b).

Record type: Article

Abstract

A range of fluoride-encapsulated octasilsesquioxane cage compounds have been prepared using the TBAF route. Our studies suggest that whilst it is relatively straightforward to prepare fluoride-encapsulated octasilsesquioxane cage compounds with adjacent sp(2) carbons, leading to a range of aryl and vinyl substituted compounds, the corresponding sp(3) carbon derivatives are more capricious, requiring an electron withdrawing group that can stabilize the cage whilst not acting as a leaving group. Analysis by X-ray crystallography and solution F-19/Si-29 NMR spectroscopy of R8T8@F- reveal very similar environments for the encapsulated fluoride octasilsesquioxane cages. Migration of a fluoride ion from inside the cage to outside the cage without breaking the T-8 framework and the possibility of encapsulating other anions within silsesquioxane cages have been also investigated.

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More information

e-pub ahead of print date: 19 December 2011
Published date: 2012
Organisations: Organic Chemistry: Synthesis, Catalysis and Flow

Identifiers

Local EPrints ID: 346001
URI: http://eprints.soton.ac.uk/id/eprint/346001
ISSN: 0300-9246
PURE UUID: 95fc580a-1dbb-420f-abbd-e5af558571d1
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

Catalogue record

Date deposited: 11 Dec 2012 11:39
Last modified: 15 Mar 2024 03:01

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Contributors

Author: Peter G. Taylor
Author: Alan R. Bassindale
Author: Youssef El Aziz
Author: Manuel Pourny
Author: Richard Stevenson
Author: Simon J. Coles ORCID iD

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