Redox Control of a Dendritic Ferrocenyl-Based Homogeneous Catalyst
The application of a dendrimer in a redox‐switchable catalytic process is reported. A monomeric and the corresponding dendritic ferrocenylphosphane ligand were used to develop well‐defined controllable catalysts with distinct redox states. The corresponding ruthenium(II) complexes catalyze the isome...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2015-01, Vol.54 (1), p.311-314 |
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| creator | Neumann, Paul Dib, Hanna Caminade, Anne-Marie Hey-Hawkins, Evamarie |
| description | The application of a dendrimer in a redox‐switchable catalytic process is reported. A monomeric and the corresponding dendritic ferrocenylphosphane ligand were used to develop well‐defined controllable catalysts with distinct redox states. The corresponding ruthenium(II) complexes catalyze the isomerization of the allylic alcohol 1‐octen‐3‐ol. By adding a chemical oxidant or reductant, it was possible to reversibly switch the catalytic activity of the complexes. On oxidation, the ferrocenium moiety withdraws electron density from the phosphane, thereby lowering its basicity. The resulting electron‐poor ruthenium center shows much lower activity for the redox isomerization and the reaction rate is markedly reduced.
Under control: Both monomeric and dendritic (see picture) ferrocenylphosphane ruthenium(II) catalysts were reversibly switched off and on by chemical oxidation and reduction during isomerization of the allylic alcohol 1‐octen‐3‐ol. This outcome is mainly due to electronic communication between the redox‐active unit and the catalytic center. Such redox control could facilitate the development of catalysts with orthogonal activity for different substrates. |
| doi_str_mv | 10.1002/anie.201408314 |
| format | Article |
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Under control: Both monomeric and dendritic (see picture) ferrocenylphosphane ruthenium(II) catalysts were reversibly switched off and on by chemical oxidation and reduction during isomerization of the allylic alcohol 1‐octen‐3‐ol. This outcome is mainly due to electronic communication between the redox‐active unit and the catalytic center. Such redox control could facilitate the development of catalysts with orthogonal activity for different substrates.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.201408314</identifier><identifier>PMID: 25414092</identifier><identifier>CODEN: ACIEAY</identifier><language>eng</language><publisher>Weinheim: WILEY-VCH Verlag</publisher><subject>Alcohols ; Basicity ; Catalysis ; Catalysts ; Catalytic activity ; Chemical Sciences ; Coordination chemistry ; Dendrimers ; Electron density ; Electronics ; ferrocene ; homogeneous catalysis ; Isomerization ; Oxidants ; Oxidation ; Oxidizing agents ; phosphanes ; redox-switchable catalysis ; Reducing agents ; Reduction ; Ruthenium ; Ruthenium compounds ; Stability</subject><ispartof>Angewandte Chemie International Edition, 2015-01, Vol.54 (1), p.311-314</ispartof><rights>2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><rights>2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>Copyright Wiley Subscription Services, Inc. Jan 2015</rights><rights>Distributed under a Creative Commons Attribution 4.0 International License</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c6094-5a00be4309cc0989aba8eb210c0049f3a843d423d40f1e6bfa8c6e58a1e6ecaf3</citedby><cites>FETCH-LOGICAL-c6094-5a00be4309cc0989aba8eb210c0049f3a843d423d40f1e6bfa8c6e58a1e6ecaf3</cites><orcidid>0000-0001-8487-3578 ; 0000-0003-4267-0603</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fanie.201408314$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.201408314$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>230,314,776,780,881,1411,27901,27902,45550,45551</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/25414092$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://hal.science/hal-01923206$$DView record in HAL$$Hfree_for_read</backlink></links><search><creatorcontrib>Neumann, Paul</creatorcontrib><creatorcontrib>Dib, Hanna</creatorcontrib><creatorcontrib>Caminade, Anne-Marie</creatorcontrib><creatorcontrib>Hey-Hawkins, Evamarie</creatorcontrib><title>Redox Control of a Dendritic Ferrocenyl-Based Homogeneous Catalyst</title><title>Angewandte Chemie International Edition</title><addtitle>Angew. Chem. Int. Ed</addtitle><description>The application of a dendrimer in a redox‐switchable catalytic process is reported. A monomeric and the corresponding dendritic ferrocenylphosphane ligand were used to develop well‐defined controllable catalysts with distinct redox states. The corresponding ruthenium(II) complexes catalyze the isomerization of the allylic alcohol 1‐octen‐3‐ol. By adding a chemical oxidant or reductant, it was possible to reversibly switch the catalytic activity of the complexes. On oxidation, the ferrocenium moiety withdraws electron density from the phosphane, thereby lowering its basicity. The resulting electron‐poor ruthenium center shows much lower activity for the redox isomerization and the reaction rate is markedly reduced.
Under control: Both monomeric and dendritic (see picture) ferrocenylphosphane ruthenium(II) catalysts were reversibly switched off and on by chemical oxidation and reduction during isomerization of the allylic alcohol 1‐octen‐3‐ol. This outcome is mainly due to electronic communication between the redox‐active unit and the catalytic center. Such redox control could facilitate the development of catalysts with orthogonal activity for different substrates.</description><subject>Alcohols</subject><subject>Basicity</subject><subject>Catalysis</subject><subject>Catalysts</subject><subject>Catalytic activity</subject><subject>Chemical Sciences</subject><subject>Coordination chemistry</subject><subject>Dendrimers</subject><subject>Electron density</subject><subject>Electronics</subject><subject>ferrocene</subject><subject>homogeneous catalysis</subject><subject>Isomerization</subject><subject>Oxidants</subject><subject>Oxidation</subject><subject>Oxidizing agents</subject><subject>phosphanes</subject><subject>redox-switchable catalysis</subject><subject>Reducing agents</subject><subject>Reduction</subject><subject>Ruthenium</subject><subject>Ruthenium compounds</subject><subject>Stability</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2015</creationdate><recordtype>article</recordtype><recordid>eNqFkc1v0zAYhy3ExMbgyhFF4jIOKa8_4tjHtmztUDXQBGLiYjnOG8hI42GnsP73c8moEAd2sPyh5_fIr36EvKAwoQDsje1bnDCgAhSn4hE5ogWjOS9L_jidBed5qQp6SJ7GeJ14pUA-IYesECmh2RGZXWLtb7O574fgu8w3mc3eYl-HdmhddoYheIf9tstnNmKdLf3af8Ue_SZmczvYbhuHZ-SgsV3E5_f7Mfl0dvpxvsxX7xfn8-kqdxK0yAsLUKHgoJ0DrbStrMKKUXAAQjfcKsFrwdKChqKsGqucxELZdEFnG35MXo_eb7YzN6Fd27A13rZmOV2Z3RtQzTgD-ZMm9mRkb4L_scE4mHUbHXad_f13Q0sArSln-mFUCiYpV0Im9NU_6LXfhD4NbVghJVWKFv-lkguUpFBAoiYj5YKPMWCzH4mC2VVrdtWafbUp8PJeu6nWWO_xP10mQI_Ar7bD7QM6M704P_1bno_ZNg54u8_a8N3IkpeF-XyxMFcfLmHx7suVmfE7WQu7aw</recordid><startdate>20150102</startdate><enddate>20150102</enddate><creator>Neumann, Paul</creator><creator>Dib, Hanna</creator><creator>Caminade, Anne-Marie</creator><creator>Hey-Hawkins, Evamarie</creator><general>WILEY-VCH Verlag</general><general>WILEY‐VCH Verlag</general><general>Wiley Subscription Services, Inc</general><general>Wiley-VCH Verlag</general><scope>BSCLL</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TM</scope><scope>K9.</scope><scope>7X8</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>1XC</scope><orcidid>https://orcid.org/0000-0001-8487-3578</orcidid><orcidid>https://orcid.org/0000-0003-4267-0603</orcidid></search><sort><creationdate>20150102</creationdate><title>Redox Control of a Dendritic Ferrocenyl-Based Homogeneous Catalyst</title><author>Neumann, Paul ; Dib, Hanna ; Caminade, Anne-Marie ; Hey-Hawkins, Evamarie</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c6094-5a00be4309cc0989aba8eb210c0049f3a843d423d40f1e6bfa8c6e58a1e6ecaf3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2015</creationdate><topic>Alcohols</topic><topic>Basicity</topic><topic>Catalysis</topic><topic>Catalysts</topic><topic>Catalytic activity</topic><topic>Chemical Sciences</topic><topic>Coordination chemistry</topic><topic>Dendrimers</topic><topic>Electron density</topic><topic>Electronics</topic><topic>ferrocene</topic><topic>homogeneous catalysis</topic><topic>Isomerization</topic><topic>Oxidants</topic><topic>Oxidation</topic><topic>Oxidizing agents</topic><topic>phosphanes</topic><topic>redox-switchable catalysis</topic><topic>Reducing agents</topic><topic>Reduction</topic><topic>Ruthenium</topic><topic>Ruthenium compounds</topic><topic>Stability</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Neumann, Paul</creatorcontrib><creatorcontrib>Dib, Hanna</creatorcontrib><creatorcontrib>Caminade, Anne-Marie</creatorcontrib><creatorcontrib>Hey-Hawkins, Evamarie</creatorcontrib><collection>Istex</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Hyper Article en Ligne (HAL)</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Neumann, Paul</au><au>Dib, Hanna</au><au>Caminade, Anne-Marie</au><au>Hey-Hawkins, Evamarie</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Redox Control of a Dendritic Ferrocenyl-Based Homogeneous Catalyst</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew. Chem. Int. Ed</addtitle><date>2015-01-02</date><risdate>2015</risdate><volume>54</volume><issue>1</issue><spage>311</spage><epage>314</epage><pages>311-314</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><coden>ACIEAY</coden><abstract>The application of a dendrimer in a redox‐switchable catalytic process is reported. A monomeric and the corresponding dendritic ferrocenylphosphane ligand were used to develop well‐defined controllable catalysts with distinct redox states. The corresponding ruthenium(II) complexes catalyze the isomerization of the allylic alcohol 1‐octen‐3‐ol. By adding a chemical oxidant or reductant, it was possible to reversibly switch the catalytic activity of the complexes. On oxidation, the ferrocenium moiety withdraws electron density from the phosphane, thereby lowering its basicity. The resulting electron‐poor ruthenium center shows much lower activity for the redox isomerization and the reaction rate is markedly reduced.
Under control: Both monomeric and dendritic (see picture) ferrocenylphosphane ruthenium(II) catalysts were reversibly switched off and on by chemical oxidation and reduction during isomerization of the allylic alcohol 1‐octen‐3‐ol. This outcome is mainly due to electronic communication between the redox‐active unit and the catalytic center. Such redox control could facilitate the development of catalysts with orthogonal activity for different substrates.</abstract><cop>Weinheim</cop><pub>WILEY-VCH Verlag</pub><pmid>25414092</pmid><doi>10.1002/anie.201408314</doi><tpages>4</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0001-8487-3578</orcidid><orcidid>https://orcid.org/0000-0003-4267-0603</orcidid></addata></record> |
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| subjects | Alcohols Basicity Catalysis Catalysts Catalytic activity Chemical Sciences Coordination chemistry Dendrimers Electron density Electronics ferrocene homogeneous catalysis Isomerization Oxidants Oxidation Oxidizing agents phosphanes redox-switchable catalysis Reducing agents Reduction Ruthenium Ruthenium compounds Stability |
| title | Redox Control of a Dendritic Ferrocenyl-Based Homogeneous Catalyst |
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