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Tunable Latency of Hydrosilylation Catalyst by Ligand Density on Nanoparticle Supports
Functionalizing inorganic particles with organic ligands is a common technique for heterogenizing organometallic catalysts. We describe how coordinating molecular platinum to silica nanoparticles functionalized with a high density of norbornene ligands causes unexpected latency of the catalytic acti...
Autores principales: | , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2022
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10107349/ https://www.ncbi.nlm.nih.gov/pubmed/36454923 http://dx.doi.org/10.1002/anie.202214267 |
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author | Miller, Susannah A. Guironnet, Damien |
author_facet | Miller, Susannah A. Guironnet, Damien |
author_sort | Miller, Susannah A. |
collection | PubMed |
description | Functionalizing inorganic particles with organic ligands is a common technique for heterogenizing organometallic catalysts. We describe how coordinating molecular platinum to silica nanoparticles functionalized with a high density of norbornene ligands causes unexpected latency of the catalytic activity in hydrosilylation reactions when compared to an identical reaction in which the norbornene is not tethered (2 % vs 97 % conversion in 1 h). Performing the hydrosilylation at elevated temperature (70 °C) suppresses this activity delay, suggesting the usefulness of this technique towards temperature‐triggered catalysis. We demonstrate that this latency is related to ligand density on the particle surface, chemical structure of the norbornene, and silica nanoparticle topology. We also establish the benefit of this latency for triggered curing of silicone elastomers. Overall, our work establishes the non‐innocent role of inorganic supports when functionalized with organometallic complexes. |
format | Online Article Text |
id | pubmed-10107349 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-101073492023-04-18 Tunable Latency of Hydrosilylation Catalyst by Ligand Density on Nanoparticle Supports Miller, Susannah A. Guironnet, Damien Angew Chem Int Ed Engl Research Articles Functionalizing inorganic particles with organic ligands is a common technique for heterogenizing organometallic catalysts. We describe how coordinating molecular platinum to silica nanoparticles functionalized with a high density of norbornene ligands causes unexpected latency of the catalytic activity in hydrosilylation reactions when compared to an identical reaction in which the norbornene is not tethered (2 % vs 97 % conversion in 1 h). Performing the hydrosilylation at elevated temperature (70 °C) suppresses this activity delay, suggesting the usefulness of this technique towards temperature‐triggered catalysis. We demonstrate that this latency is related to ligand density on the particle surface, chemical structure of the norbornene, and silica nanoparticle topology. We also establish the benefit of this latency for triggered curing of silicone elastomers. Overall, our work establishes the non‐innocent role of inorganic supports when functionalized with organometallic complexes. John Wiley and Sons Inc. 2022-12-22 2023-01-26 /pmc/articles/PMC10107349/ /pubmed/36454923 http://dx.doi.org/10.1002/anie.202214267 Text en © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH https://creativecommons.org/licenses/by-nc-nd/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ (https://creativecommons.org/licenses/by-nc-nd/4.0/) License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made. |
spellingShingle | Research Articles Miller, Susannah A. Guironnet, Damien Tunable Latency of Hydrosilylation Catalyst by Ligand Density on Nanoparticle Supports |
title | Tunable Latency of Hydrosilylation Catalyst by Ligand Density on Nanoparticle Supports |
title_full | Tunable Latency of Hydrosilylation Catalyst by Ligand Density on Nanoparticle Supports |
title_fullStr | Tunable Latency of Hydrosilylation Catalyst by Ligand Density on Nanoparticle Supports |
title_full_unstemmed | Tunable Latency of Hydrosilylation Catalyst by Ligand Density on Nanoparticle Supports |
title_short | Tunable Latency of Hydrosilylation Catalyst by Ligand Density on Nanoparticle Supports |
title_sort | tunable latency of hydrosilylation catalyst by ligand density on nanoparticle supports |
topic | Research Articles |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10107349/ https://www.ncbi.nlm.nih.gov/pubmed/36454923 http://dx.doi.org/10.1002/anie.202214267 |
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