Pyridine modifications regulate the electronics and reactivity of Fe-pyridinophane complexes
12-Membered pyridinophanes are the focus of many studies as biological mimics, chelators, and catalytic precursors. Therefore, the desire to tune the reactivity of pyridinophanes to better control the applications of derivative metal complexes has inspired many structure-activity relationship studie...
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Veröffentlicht in: | Dalton transactions : an international journal of inorganic chemistry 2023-01, Vol.52 (4), p.892-91 |
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description | 12-Membered pyridinophanes are the focus of many studies as biological mimics, chelators, and catalytic precursors. Therefore, the desire to tune the reactivity of pyridinophanes to better control the applications of derivative metal complexes has inspired many structure-activity relationship studies. However, the separation of structural
versus
electronic changes imparted by ligand modification has made these structure-activity relationship studies of transition metal catalysts challenging to define. In this work we show that 4-substitution of the pyridine ring in 12-membered tetra-aza pyridinophanes successfully provides a regulatory handle on the electronic properties of the metal center and, therefore, the catalytic C-C coupling activity of the respective iron complexes. The C-C coupling reaction catalyzed by Fe(
L1-L6
) provides a range of yields (32-58%) that directly correlate with iron redox potentials (Δ
E
1/2
= 152 mV) and metal binding constants (Δlog
β
= 3.45), while the geometry of the complexes was virtually indistinguishable. These are the first results to definitively show the redox potential and metal binding as independent properties from the coordination chemistry in one ligand series. Adjustments to these chemical properties were then shown to provide a regulatory handle for the C-C coupling reactivity tuned
via
pyridine substitution in pyridinophanes.
Substitution of the pyridine ring in 12-membered tetra-aza pyridinophanes successfully provides a regulatory handle on log
β
and the Fe(
ii
/
iii
) redox couple. A C-C coupling reaction is used as a readout of these changes to the ligand. |
doi_str_mv | 10.1039/d2dt03485a |
format | Article |
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versus
electronic changes imparted by ligand modification has made these structure-activity relationship studies of transition metal catalysts challenging to define. In this work we show that 4-substitution of the pyridine ring in 12-membered tetra-aza pyridinophanes successfully provides a regulatory handle on the electronic properties of the metal center and, therefore, the catalytic C-C coupling activity of the respective iron complexes. The C-C coupling reaction catalyzed by Fe(
L1-L6
) provides a range of yields (32-58%) that directly correlate with iron redox potentials (Δ
E
1/2
= 152 mV) and metal binding constants (Δlog
β
= 3.45), while the geometry of the complexes was virtually indistinguishable. These are the first results to definitively show the redox potential and metal binding as independent properties from the coordination chemistry in one ligand series. Adjustments to these chemical properties were then shown to provide a regulatory handle for the C-C coupling reactivity tuned
via
pyridine substitution in pyridinophanes.
Substitution of the pyridine ring in 12-membered tetra-aza pyridinophanes successfully provides a regulatory handle on log
β
and the Fe(
ii
/
iii
) redox couple. A C-C coupling reaction is used as a readout of these changes to the ligand.</description><identifier>ISSN: 1477-9226</identifier><identifier>EISSN: 1477-9234</identifier><identifier>DOI: 10.1039/d2dt03485a</identifier><identifier>PMID: 36537287</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Binding ; Chelating Agents ; Chemical properties ; Coordination Complexes - chemistry ; Coordination compounds ; Coupling ; Iron ; Iron - chemistry ; Ligands ; Pyridines ; Reactivity ; Substitution reactions ; Transition Elements ; Transition metals</subject><ispartof>Dalton transactions : an international journal of inorganic chemistry, 2023-01, Vol.52 (4), p.892-91</ispartof><rights>Copyright Royal Society of Chemistry 2023</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c323t-523d9c2e15d2753b9cb877db1dd51733a38a7afe28c110e3ae2289c6ffe6f7913</citedby><cites>FETCH-LOGICAL-c323t-523d9c2e15d2753b9cb877db1dd51733a38a7afe28c110e3ae2289c6ffe6f7913</cites><orcidid>0000-0002-0976-2680 ; 0000-0002-9027-0201 ; 0000-0001-8816-7646</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,315,782,786,887,27931,27932</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/36537287$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Mekhail, Magy A</creatorcontrib><creatorcontrib>Pota, Kristof</creatorcontrib><creatorcontrib>Kharel, Sugam</creatorcontrib><creatorcontrib>Freire, David M</creatorcontrib><creatorcontrib>Green, Kayla N</creatorcontrib><title>Pyridine modifications regulate the electronics and reactivity of Fe-pyridinophane complexes</title><title>Dalton transactions : an international journal of inorganic chemistry</title><addtitle>Dalton Trans</addtitle><description>12-Membered pyridinophanes are the focus of many studies as biological mimics, chelators, and catalytic precursors. Therefore, the desire to tune the reactivity of pyridinophanes to better control the applications of derivative metal complexes has inspired many structure-activity relationship studies. However, the separation of structural
versus
electronic changes imparted by ligand modification has made these structure-activity relationship studies of transition metal catalysts challenging to define. In this work we show that 4-substitution of the pyridine ring in 12-membered tetra-aza pyridinophanes successfully provides a regulatory handle on the electronic properties of the metal center and, therefore, the catalytic C-C coupling activity of the respective iron complexes. The C-C coupling reaction catalyzed by Fe(
L1-L6
) provides a range of yields (32-58%) that directly correlate with iron redox potentials (Δ
E
1/2
= 152 mV) and metal binding constants (Δlog
β
= 3.45), while the geometry of the complexes was virtually indistinguishable. These are the first results to definitively show the redox potential and metal binding as independent properties from the coordination chemistry in one ligand series. Adjustments to these chemical properties were then shown to provide a regulatory handle for the C-C coupling reactivity tuned
via
pyridine substitution in pyridinophanes.
Substitution of the pyridine ring in 12-membered tetra-aza pyridinophanes successfully provides a regulatory handle on log
β
and the Fe(
ii
/
iii
) redox couple. A C-C coupling reaction is used as a readout of these changes to the ligand.</description><subject>Binding</subject><subject>Chelating Agents</subject><subject>Chemical properties</subject><subject>Coordination Complexes - chemistry</subject><subject>Coordination compounds</subject><subject>Coupling</subject><subject>Iron</subject><subject>Iron - chemistry</subject><subject>Ligands</subject><subject>Pyridines</subject><subject>Reactivity</subject><subject>Substitution reactions</subject><subject>Transition Elements</subject><subject>Transition metals</subject><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><recordid>eNpdkUtLJDEUhcOg-OhxM3ulYDYilJPkdlWqViK-QXAWzk4I6eSWHamqlElKpv-90db2sUrgfHycyyHkF6OHjEL9x3ATKUyrQv0gW2wqRF5zmK6t_rzcJNshPFDKOS34BtmEsgDBK7FF7v4uvDW2x6xzxjZWq2hdHzKP92OrImZxjhm2qKN3vdUhU71JodLRPtm4yFyTnWM-LCVumKtk0q4bWvyP4SdZb1QbcOftnZB_52e3J5f59c3F1cnxda6BQ8wLDqbWHFlhuChgVutZJYSZMWMKJgAUVEqoBnmlGaMICjmval02DZaNqBlMyNHSO4yzDo3GPnrVysHbTvmFdMrKr0lv5_LePUlGawqMvRj23wzePY4Youxs0Ni26R43Bpl6lYxPRcIn5Pc39MGNvk_3JaqsyoJBWSfqYElp70Lw2KzaMCpfVpOn_PT2dbXjBO997r9C32dKwO4S8EGv0o_Z4Rm3tZ5Y</recordid><startdate>20230124</startdate><enddate>20230124</enddate><creator>Mekhail, Magy A</creator><creator>Pota, Kristof</creator><creator>Kharel, Sugam</creator><creator>Freire, David M</creator><creator>Green, Kayla N</creator><general>Royal Society of Chemistry</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope><scope>7X8</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0002-0976-2680</orcidid><orcidid>https://orcid.org/0000-0002-9027-0201</orcidid><orcidid>https://orcid.org/0000-0001-8816-7646</orcidid></search><sort><creationdate>20230124</creationdate><title>Pyridine modifications regulate the electronics and reactivity of Fe-pyridinophane complexes</title><author>Mekhail, Magy A ; Pota, Kristof ; Kharel, Sugam ; Freire, David M ; Green, Kayla N</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c323t-523d9c2e15d2753b9cb877db1dd51733a38a7afe28c110e3ae2289c6ffe6f7913</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><topic>Binding</topic><topic>Chelating Agents</topic><topic>Chemical properties</topic><topic>Coordination Complexes - chemistry</topic><topic>Coordination compounds</topic><topic>Coupling</topic><topic>Iron</topic><topic>Iron - chemistry</topic><topic>Ligands</topic><topic>Pyridines</topic><topic>Reactivity</topic><topic>Substitution reactions</topic><topic>Transition Elements</topic><topic>Transition metals</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Mekhail, Magy A</creatorcontrib><creatorcontrib>Pota, Kristof</creatorcontrib><creatorcontrib>Kharel, Sugam</creatorcontrib><creatorcontrib>Freire, David M</creatorcontrib><creatorcontrib>Green, Kayla N</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Mekhail, Magy A</au><au>Pota, Kristof</au><au>Kharel, Sugam</au><au>Freire, David M</au><au>Green, Kayla N</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Pyridine modifications regulate the electronics and reactivity of Fe-pyridinophane complexes</atitle><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle><addtitle>Dalton Trans</addtitle><date>2023-01-24</date><risdate>2023</risdate><volume>52</volume><issue>4</issue><spage>892</spage><epage>91</epage><pages>892-91</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><abstract>12-Membered pyridinophanes are the focus of many studies as biological mimics, chelators, and catalytic precursors. Therefore, the desire to tune the reactivity of pyridinophanes to better control the applications of derivative metal complexes has inspired many structure-activity relationship studies. However, the separation of structural
versus
electronic changes imparted by ligand modification has made these structure-activity relationship studies of transition metal catalysts challenging to define. In this work we show that 4-substitution of the pyridine ring in 12-membered tetra-aza pyridinophanes successfully provides a regulatory handle on the electronic properties of the metal center and, therefore, the catalytic C-C coupling activity of the respective iron complexes. The C-C coupling reaction catalyzed by Fe(
L1-L6
) provides a range of yields (32-58%) that directly correlate with iron redox potentials (Δ
E
1/2
= 152 mV) and metal binding constants (Δlog
β
= 3.45), while the geometry of the complexes was virtually indistinguishable. These are the first results to definitively show the redox potential and metal binding as independent properties from the coordination chemistry in one ligand series. Adjustments to these chemical properties were then shown to provide a regulatory handle for the C-C coupling reactivity tuned
via
pyridine substitution in pyridinophanes.
Substitution of the pyridine ring in 12-membered tetra-aza pyridinophanes successfully provides a regulatory handle on log
β
and the Fe(
ii
/
iii
) redox couple. A C-C coupling reaction is used as a readout of these changes to the ligand.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>36537287</pmid><doi>10.1039/d2dt03485a</doi><tpages>1</tpages><orcidid>https://orcid.org/0000-0002-0976-2680</orcidid><orcidid>https://orcid.org/0000-0002-9027-0201</orcidid><orcidid>https://orcid.org/0000-0001-8816-7646</orcidid></addata></record> |
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subjects | Binding Chelating Agents Chemical properties Coordination Complexes - chemistry Coordination compounds Coupling Iron Iron - chemistry Ligands Pyridines Reactivity Substitution reactions Transition Elements Transition metals |
title | Pyridine modifications regulate the electronics and reactivity of Fe-pyridinophane complexes |
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