Publikation: Metathesis catalysts in confining reaction fields-confinement effects vs. surface effects
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2010
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Dalton Trans.. 2010, 39(2), pp. 577-584. ISSN 1477-9226. eISSN 1477-9234. Available under: doi: 10.1039/B911795B
Zusammenfassung
It has been recognized previously that inside nanosized cavities like in mesoporous materials a small ensemble situation can be realized. The limited number of reactants per confinement leads to unusual chemical behaviour whenever inter- vs. intramolecular pathways compete against each other. Therefore, the metathesis reaction might represent a chemical process for which the product distribution is influenced by a confining reaction field. In the current paper we report about the unusual reactivity of the Grubbs generation I catalyst inside mesoporous silica materials. It has been observed that due to a combination of confinement and surface effects the Grubbs catalyst is not stable inside small pores. It quickly rearranges to a variety of unexpected products. However, the undesired deactivation of the catalyst can be prohibited by surface modification of the silica surfaces.
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540 Chemie
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matrix-isolation spectroscopy, single-molecule spectroscopy, olefin metathesis, nanoporous materials, hybride materials, porous materials, silica, enantioselectivity, zeolite, crystal
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POLARZ, Sebastian, B. VOELKER, Felix JEREMIAS, 2010. Metathesis catalysts in confining reaction fields-confinement effects vs. surface effects. In: Dalton Trans.. 2010, 39(2), pp. 577-584. ISSN 1477-9226. eISSN 1477-9234. Available under: doi: 10.1039/B911795BBibTex
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year={2010},
doi={10.1039/B911795B},
title={Metathesis catalysts in confining reaction fields-confinement effects vs. surface effects},
number={2},
volume={39},
issn={1477-9226},
journal={Dalton Trans.},
pages={577--584},
author={Polarz, Sebastian and Voelker, B. and Jeremias, Felix}
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<dcterms:abstract xml:lang="eng">It has been recognized previously that inside nanosized cavities like in mesoporous materials a small ensemble situation can be realized. The limited number of reactants per confinement leads to unusual chemical behaviour whenever inter- vs. intramolecular pathways compete against each other. Therefore, the metathesis reaction might represent a chemical process for which the product distribution is influenced by a confining reaction field. In the current paper we report about the unusual reactivity of the Grubbs generation I catalyst inside mesoporous silica materials. It has been observed that due to a combination of confinement and surface effects the Grubbs catalyst is not stable inside small pores. It quickly rearranges to a variety of unexpected products. However, the undesired deactivation of the catalyst can be prohibited by surface modification of the silica surfaces.</dcterms:abstract>
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