Chemical reactions at the graphitic step-edge: changes in product distribution of catalytic reactions as a tool to explore the environment within carbon nanoreactors

A series of explorative cross-coupling reactions have been developed to investigate the local nanoscale environment around catalytically active Pd(II)complexes encapsulated within hollow graphitised nanofiber (GNF). Two new fullerene-containing and fullerene-free Pd(II)Salen catalysts have been synt...

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Main Authors: Lebedeva, Maria A., Chamberlain, Thomas W., Thomas, Alice, Thomas, Bradley E., Stoppiello, Craig T., Volkova, Evgeniya, Suyetin, Mikhail, Khlobystov, Andrei N.
Format: Article
Published: Royal Society of Chemistry 2016
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Online Access:https://eprints.nottingham.ac.uk/45601/
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author Lebedeva, Maria A.
Chamberlain, Thomas W.
Thomas, Alice
Thomas, Bradley E.
Stoppiello, Craig T.
Volkova, Evgeniya
Suyetin, Mikhail
Khlobystov, Andrei N.
author_facet Lebedeva, Maria A.
Chamberlain, Thomas W.
Thomas, Alice
Thomas, Bradley E.
Stoppiello, Craig T.
Volkova, Evgeniya
Suyetin, Mikhail
Khlobystov, Andrei N.
author_sort Lebedeva, Maria A.
building Nottingham Research Data Repository
collection Online Access
description A series of explorative cross-coupling reactions have been developed to investigate the local nanoscale environment around catalytically active Pd(II)complexes encapsulated within hollow graphitised nanofiber (GNF). Two new fullerene-containing and fullerene-free Pd(II)Salen catalysts have been synthesised, and their activity and selectivity towards different substrates has been explored in nanoreactors. The catalysts not only show a significant increase in activity and stability upon heterogenisation at the graphitic step-edges inside the GNF channel, but also exhibit a change in selectivity affected by the confinement which alters the distribution of isomeric products of the reaction. Furthermore, the observed selectivity changes reveal unprecedented details regarding the location and orientation of the catalyst molecules inside the GNF nanoreactor, inaccessible by any spectroscopic or microscopic techniques, thus shedding light on the precise reaction environment inside the molecular catalyst-GNF nanoreactor. Keywords: nanoreactor, catalysis, fullerene, salen, cross-coupling
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publishDate 2016
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spelling nottingham-456012020-05-04T17:52:14Z https://eprints.nottingham.ac.uk/45601/ Chemical reactions at the graphitic step-edge: changes in product distribution of catalytic reactions as a tool to explore the environment within carbon nanoreactors Lebedeva, Maria A. Chamberlain, Thomas W. Thomas, Alice Thomas, Bradley E. Stoppiello, Craig T. Volkova, Evgeniya Suyetin, Mikhail Khlobystov, Andrei N. A series of explorative cross-coupling reactions have been developed to investigate the local nanoscale environment around catalytically active Pd(II)complexes encapsulated within hollow graphitised nanofiber (GNF). Two new fullerene-containing and fullerene-free Pd(II)Salen catalysts have been synthesised, and their activity and selectivity towards different substrates has been explored in nanoreactors. The catalysts not only show a significant increase in activity and stability upon heterogenisation at the graphitic step-edges inside the GNF channel, but also exhibit a change in selectivity affected by the confinement which alters the distribution of isomeric products of the reaction. Furthermore, the observed selectivity changes reveal unprecedented details regarding the location and orientation of the catalyst molecules inside the GNF nanoreactor, inaccessible by any spectroscopic or microscopic techniques, thus shedding light on the precise reaction environment inside the molecular catalyst-GNF nanoreactor. Keywords: nanoreactor, catalysis, fullerene, salen, cross-coupling Royal Society of Chemistry 2016-05-12 Article PeerReviewed Lebedeva, Maria A., Chamberlain, Thomas W., Thomas, Alice, Thomas, Bradley E., Stoppiello, Craig T., Volkova, Evgeniya, Suyetin, Mikhail and Khlobystov, Andrei N. (2016) Chemical reactions at the graphitic step-edge: changes in product distribution of catalytic reactions as a tool to explore the environment within carbon nanoreactors. Nanoscale, 8 (22). pp. 11727-11737. ISSN 2040-3372 nanoreactor catalysis fullerene salen cross-coupling http://pubs.rsc.org/en/content/articlelanding/2016/nr/c6nr03360a#!divAbstract doi:10.1039/C6NR03360A doi:10.1039/C6NR03360A
spellingShingle nanoreactor
catalysis
fullerene
salen
cross-coupling
Lebedeva, Maria A.
Chamberlain, Thomas W.
Thomas, Alice
Thomas, Bradley E.
Stoppiello, Craig T.
Volkova, Evgeniya
Suyetin, Mikhail
Khlobystov, Andrei N.
Chemical reactions at the graphitic step-edge: changes in product distribution of catalytic reactions as a tool to explore the environment within carbon nanoreactors
title Chemical reactions at the graphitic step-edge: changes in product distribution of catalytic reactions as a tool to explore the environment within carbon nanoreactors
title_full Chemical reactions at the graphitic step-edge: changes in product distribution of catalytic reactions as a tool to explore the environment within carbon nanoreactors
title_fullStr Chemical reactions at the graphitic step-edge: changes in product distribution of catalytic reactions as a tool to explore the environment within carbon nanoreactors
title_full_unstemmed Chemical reactions at the graphitic step-edge: changes in product distribution of catalytic reactions as a tool to explore the environment within carbon nanoreactors
title_short Chemical reactions at the graphitic step-edge: changes in product distribution of catalytic reactions as a tool to explore the environment within carbon nanoreactors
title_sort chemical reactions at the graphitic step-edge: changes in product distribution of catalytic reactions as a tool to explore the environment within carbon nanoreactors
topic nanoreactor
catalysis
fullerene
salen
cross-coupling
url https://eprints.nottingham.ac.uk/45601/
https://eprints.nottingham.ac.uk/45601/
https://eprints.nottingham.ac.uk/45601/