A New Type of Valence Tautomerism in Cobalt Dioxolene Complexes – Temperature‐Induced Transition from a Cobalt(III) Catecholate to a Low‐Spin Cobalt(II) Semiquinonate State
The synthesis and characterization of the monocationic cobalt(III) catecholate complex [Co(L‐N4tBu2)(Cl2cat)]+ (L‐N4tBu2=N,N’‐Di‐tert.‐butyl‐2,11‐diaza[3.3](2,6)pyridinophane, Cl2cat2−=4,5‐dichlorocatecholate) are presented. The complex exhibits valence tautomeric properties in solution; but, in con...
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| Veröffentlicht in: | Chemistry : a European journal 2023-05, Vol.29 (30), p.e202300091-n/a |
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| creator | Metzger, Christoph Dolai, Ramapada Reh, Sabine Kelm, Harald Schmitz, Markus Oelkers, Benjamin Sawall, Mathias Neymeyr, Klaus Krüger, Hans‐Jörg |
| description | The synthesis and characterization of the monocationic cobalt(III) catecholate complex [Co(L‐N4tBu2)(Cl2cat)]+ (L‐N4tBu2=N,N’‐Di‐tert.‐butyl‐2,11‐diaza[3.3](2,6)pyridinophane, Cl2cat2−=4,5‐dichlorocatecholate) are presented. The complex exhibits valence tautomeric properties in solution; but, in contrast to the usually observed conversion from a cobalt(III) catecholate to a high‐spin cobalt(II) semiquinonate state, valence tautomerism of [Co(L‐N4tBu2)(Cl2cat)]+ leads to the formation of a low‐spin cobalt(II) semiquinonate complex upon raising the temperature. This new type of valence tautomerism for a cobalt dioxolene complex has been unambiguously established by a detailed spectroscopic investigation using variable‐temperature NMR, IR and UV‐Vis‐NIR spectroscopy. Determination of the enthalpies and entropies characterizing the valence tautomeric equilibria in various solutions shows that the influence of the solvent is almost exclusively entropic.
A novel twist in temperature‐induced switching of electronic states in cobalt dioxolene complexes: Structural, magnetic, and spectroscopic results demonstrate that valence tautomerism can occur by converting a cobalt(III) catecholate into a low‐spin cobalt(II) semiquinonate complex instead of the usual high‐spin complex. |
| doi_str_mv | 10.1002/chem.202300091 |
| format | Article |
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A novel twist in temperature‐induced switching of electronic states in cobalt dioxolene complexes: Structural, magnetic, and spectroscopic results demonstrate that valence tautomerism can occur by converting a cobalt(III) catecholate into a low‐spin cobalt(II) semiquinonate complex instead of the usual high‐spin complex.</description><identifier>ISSN: 0947-6539</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/chem.202300091</identifier><identifier>PMID: 36808779</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>catecholate ligand ; Chemistry ; Cobalt ; Enthalpy ; NMR ; Nuclear magnetic resonance ; semiquinonate ligand ; Spectroscopy ; Tautomerism ; tetraazamacrocyclic ligand ; valence tautomerism</subject><ispartof>Chemistry : a European journal, 2023-05, Vol.29 (30), p.e202300091-n/a</ispartof><rights>2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH</rights><rights>2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.</rights><rights>2023. This article is published under http://creativecommons.org/licenses/by-nc-nd/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c4131-5c6f5611e1054bb14b2f445eed03befc194b40b8ef0f272df70b9f40868cd663</citedby><cites>FETCH-LOGICAL-c4131-5c6f5611e1054bb14b2f445eed03befc194b40b8ef0f272df70b9f40868cd663</cites><orcidid>0000-0003-2909-1287 ; 0000-0001-9264-9437 ; 0000-0002-1464-2851 ; 0000-0001-7415-9012 ; 0000-0002-8652-2154</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%2Fchem.202300091$$EPDF$$P50$$Gwiley$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fchem.202300091$$EHTML$$P50$$Gwiley$$Hfree_for_read</linktohtml><link.rule.ids>314,776,780,1411,27901,27902,45550,45551</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/36808779$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Metzger, Christoph</creatorcontrib><creatorcontrib>Dolai, Ramapada</creatorcontrib><creatorcontrib>Reh, Sabine</creatorcontrib><creatorcontrib>Kelm, Harald</creatorcontrib><creatorcontrib>Schmitz, Markus</creatorcontrib><creatorcontrib>Oelkers, Benjamin</creatorcontrib><creatorcontrib>Sawall, Mathias</creatorcontrib><creatorcontrib>Neymeyr, Klaus</creatorcontrib><creatorcontrib>Krüger, Hans‐Jörg</creatorcontrib><title>A New Type of Valence Tautomerism in Cobalt Dioxolene Complexes – Temperature‐Induced Transition from a Cobalt(III) Catecholate to a Low‐Spin Cobalt(II) Semiquinonate State</title><title>Chemistry : a European journal</title><addtitle>Chemistry</addtitle><description>The synthesis and characterization of the monocationic cobalt(III) catecholate complex [Co(L‐N4tBu2)(Cl2cat)]+ (L‐N4tBu2=N,N’‐Di‐tert.‐butyl‐2,11‐diaza[3.3](2,6)pyridinophane, Cl2cat2−=4,5‐dichlorocatecholate) are presented. The complex exhibits valence tautomeric properties in solution; but, in contrast to the usually observed conversion from a cobalt(III) catecholate to a high‐spin cobalt(II) semiquinonate state, valence tautomerism of [Co(L‐N4tBu2)(Cl2cat)]+ leads to the formation of a low‐spin cobalt(II) semiquinonate complex upon raising the temperature. This new type of valence tautomerism for a cobalt dioxolene complex has been unambiguously established by a detailed spectroscopic investigation using variable‐temperature NMR, IR and UV‐Vis‐NIR spectroscopy. Determination of the enthalpies and entropies characterizing the valence tautomeric equilibria in various solutions shows that the influence of the solvent is almost exclusively entropic.
A novel twist in temperature‐induced switching of electronic states in cobalt dioxolene complexes: Structural, magnetic, and spectroscopic results demonstrate that valence tautomerism can occur by converting a cobalt(III) catecholate into a low‐spin cobalt(II) semiquinonate complex instead of the usual high‐spin complex.</description><subject>catecholate ligand</subject><subject>Chemistry</subject><subject>Cobalt</subject><subject>Enthalpy</subject><subject>NMR</subject><subject>Nuclear magnetic resonance</subject><subject>semiquinonate ligand</subject><subject>Spectroscopy</subject><subject>Tautomerism</subject><subject>tetraazamacrocyclic ligand</subject><subject>valence tautomerism</subject><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><sourceid>24P</sourceid><recordid>eNqF0U9v0zAYBvAIgVgZXDkiS1y6Q4r_xU6OU7axSgUOjbhGjvNay5TEmZ2o620fAYlvwkfaJ8FRS5G4cPEr2T8_tvRE0XuCVwRj-knfQbeimDKMcUZeRAuSUBIzKZKX0QJnXMYiYdlZ9Mb7-5kIxl5HZ0ykOJUyW0S_LtFX2KFiPwCyBn1XLfQaUKGm0XbgGt-hpke5rVQ7oqvGPtoAIGx0QwuP4NHz009UQDeAU-Pk4Pnpx7qvJw01KpzqfTM2tkfG2Q6pY8xyvV5foFyNoO9sGwYabTjc2F24vB1Ozy1ntoWueZia3vYz3I5hfRu9Mqr18O44z6Pi5rrIb-PNt8_r_HITa04YiRMtTCIIAYITXlWEV9RwngDUmFVgNMl4xXGVgsGGSlobiavMcJyKVNdCsPNoeYgdnH2YwI9l13gNbat6sJMvqZRpJhnnaaAf_6H3dnJ9-FxJU5JRmohUBrU6KO2s9w5MObimU25fElzOZZZzmeWpzHDhwzF2qjqoT_xPewFkB7BrWtj_J67Mb6-__A3_DTBOru8</recordid><startdate>20230526</startdate><enddate>20230526</enddate><creator>Metzger, Christoph</creator><creator>Dolai, Ramapada</creator><creator>Reh, Sabine</creator><creator>Kelm, Harald</creator><creator>Schmitz, Markus</creator><creator>Oelkers, Benjamin</creator><creator>Sawall, Mathias</creator><creator>Neymeyr, Klaus</creator><creator>Krüger, Hans‐Jörg</creator><general>Wiley Subscription Services, Inc</general><scope>24P</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>K9.</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0003-2909-1287</orcidid><orcidid>https://orcid.org/0000-0001-9264-9437</orcidid><orcidid>https://orcid.org/0000-0002-1464-2851</orcidid><orcidid>https://orcid.org/0000-0001-7415-9012</orcidid><orcidid>https://orcid.org/0000-0002-8652-2154</orcidid></search><sort><creationdate>20230526</creationdate><title>A New Type of Valence Tautomerism in Cobalt Dioxolene Complexes – Temperature‐Induced Transition from a Cobalt(III) Catecholate to a Low‐Spin Cobalt(II) Semiquinonate State</title><author>Metzger, Christoph ; Dolai, Ramapada ; Reh, Sabine ; Kelm, Harald ; Schmitz, Markus ; Oelkers, Benjamin ; Sawall, Mathias ; Neymeyr, Klaus ; Krüger, Hans‐Jörg</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c4131-5c6f5611e1054bb14b2f445eed03befc194b40b8ef0f272df70b9f40868cd663</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><topic>catecholate ligand</topic><topic>Chemistry</topic><topic>Cobalt</topic><topic>Enthalpy</topic><topic>NMR</topic><topic>Nuclear magnetic resonance</topic><topic>semiquinonate ligand</topic><topic>Spectroscopy</topic><topic>Tautomerism</topic><topic>tetraazamacrocyclic ligand</topic><topic>valence tautomerism</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Metzger, Christoph</creatorcontrib><creatorcontrib>Dolai, Ramapada</creatorcontrib><creatorcontrib>Reh, Sabine</creatorcontrib><creatorcontrib>Kelm, Harald</creatorcontrib><creatorcontrib>Schmitz, Markus</creatorcontrib><creatorcontrib>Oelkers, Benjamin</creatorcontrib><creatorcontrib>Sawall, Mathias</creatorcontrib><creatorcontrib>Neymeyr, Klaus</creatorcontrib><creatorcontrib>Krüger, Hans‐Jörg</creatorcontrib><collection>Wiley Online Library Open Access</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><jtitle>Chemistry : a European journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Metzger, Christoph</au><au>Dolai, Ramapada</au><au>Reh, Sabine</au><au>Kelm, Harald</au><au>Schmitz, Markus</au><au>Oelkers, Benjamin</au><au>Sawall, Mathias</au><au>Neymeyr, Klaus</au><au>Krüger, Hans‐Jörg</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>A New Type of Valence Tautomerism in Cobalt Dioxolene Complexes – Temperature‐Induced Transition from a Cobalt(III) Catecholate to a Low‐Spin Cobalt(II) Semiquinonate State</atitle><jtitle>Chemistry : a European journal</jtitle><addtitle>Chemistry</addtitle><date>2023-05-26</date><risdate>2023</risdate><volume>29</volume><issue>30</issue><spage>e202300091</spage><epage>n/a</epage><pages>e202300091-n/a</pages><issn>0947-6539</issn><eissn>1521-3765</eissn><abstract>The synthesis and characterization of the monocationic cobalt(III) catecholate complex [Co(L‐N4tBu2)(Cl2cat)]+ (L‐N4tBu2=N,N’‐Di‐tert.‐butyl‐2,11‐diaza[3.3](2,6)pyridinophane, Cl2cat2−=4,5‐dichlorocatecholate) are presented. The complex exhibits valence tautomeric properties in solution; but, in contrast to the usually observed conversion from a cobalt(III) catecholate to a high‐spin cobalt(II) semiquinonate state, valence tautomerism of [Co(L‐N4tBu2)(Cl2cat)]+ leads to the formation of a low‐spin cobalt(II) semiquinonate complex upon raising the temperature. This new type of valence tautomerism for a cobalt dioxolene complex has been unambiguously established by a detailed spectroscopic investigation using variable‐temperature NMR, IR and UV‐Vis‐NIR spectroscopy. Determination of the enthalpies and entropies characterizing the valence tautomeric equilibria in various solutions shows that the influence of the solvent is almost exclusively entropic.
A novel twist in temperature‐induced switching of electronic states in cobalt dioxolene complexes: Structural, magnetic, and spectroscopic results demonstrate that valence tautomerism can occur by converting a cobalt(III) catecholate into a low‐spin cobalt(II) semiquinonate complex instead of the usual high‐spin complex.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>36808779</pmid><doi>10.1002/chem.202300091</doi><tpages>11</tpages><orcidid>https://orcid.org/0000-0003-2909-1287</orcidid><orcidid>https://orcid.org/0000-0001-9264-9437</orcidid><orcidid>https://orcid.org/0000-0002-1464-2851</orcidid><orcidid>https://orcid.org/0000-0001-7415-9012</orcidid><orcidid>https://orcid.org/0000-0002-8652-2154</orcidid><oa>free_for_read</oa></addata></record> |
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| source | Wiley Online Library Journals Frontfile Complete |
| subjects | catecholate ligand Chemistry Cobalt Enthalpy NMR Nuclear magnetic resonance semiquinonate ligand Spectroscopy Tautomerism tetraazamacrocyclic ligand valence tautomerism |
| title | A New Type of Valence Tautomerism in Cobalt Dioxolene Complexes – Temperature‐Induced Transition from a Cobalt(III) Catecholate to a Low‐Spin Cobalt(II) Semiquinonate State |
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