Dinitrogen Coordination to a High‐Spin Diiron(I/II) Species
Dinitrogen coordination to iron centers underpins industrial and biological fixation in the Haber–Bosch process and by the FeM cofactors in the nitrogenase enzymes. The latter employ local high‐spin metal centers; however, iron–dinitrogen coordination chemistry remains dominated by low‐valent states...
Gespeichert in:
| Veröffentlicht in: | Angewandte Chemie International Edition 2022-05, Vol.61 (22), p.e202202329-n/a |
|---|---|
| Hauptverfasser: | , , , , , , , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | n/a |
|---|---|
| container_issue | 22 |
| container_start_page | e202202329 |
| container_title | Angewandte Chemie International Edition |
| container_volume | 61 |
| creator | Torres, Juan F. Oi, Collin H. Moseley, Ian P. El‐Sakkout, Nabila Knight, Brian J. Shearer, Jason García‐Serres, Ricardo Zadrozny, Joseph M. Murray, Leslie J. |
| description | Dinitrogen coordination to iron centers underpins industrial and biological fixation in the Haber–Bosch process and by the FeM cofactors in the nitrogenase enzymes. The latter employ local high‐spin metal centers; however, iron–dinitrogen coordination chemistry remains dominated by low‐valent states, contrasting the enzyme systems. Here, we report a high‐spin mixed‐valent cis‐(μ‐1,2‐dinitrogen)diiron(I/II) complex [(FeBr)2(μ‐N2)Lbis]− (2), where [Lbis]− is a bis(β‐diketiminate) cyclophane. Field‐applied Mössbauer spectra, dc and ac magnetic susceptibility measurements, and computational methods support a delocalized S=7/2 Fe2N2 unit with D=−5.23 cm−1 and consequent slow magnetic relaxation.
Dinitrogen coordination to multiiron complexes is instrumental in understanding the reactivity of nitrogenases cofactors. The synthesis of a high‐spin mixed‐valent cis‐(μ‐1,2‐dinitrogen)diiron(I/II) complex obtained by a one‐electron reduction of a diiron(II/II) precursor is reported. The electronic structure of the complex was studied using Mössbauer spectroscopy, SQUID magnetometry, and DFT calculations, which support a S=7/2 ground state. |
| doi_str_mv | 10.1002/anie.202202329 |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_pubme</sourceid><recordid>TN_cdi_pubmedcentral_primary_oai_pubmedcentral_nih_gov_9117494</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2641004037</sourcerecordid><originalsourceid>FETCH-LOGICAL-c5029-2283890fae28f2b6a656967282f15669a72a46b12cd1c5ec82874b0e0b0352793</originalsourceid><addsrcrecordid>eNqFkc1uEzEUhS1ERUvLliUaiU27mNS-_p0FlaK0kJEiumi7tjwTT-JqYgd7UtQdj8Az8iQ4ShugGyRLtq6_e659DkLvCR4RjOHceGdHgCEvCtUrdEQ4kJJKSV_nM6O0lIqTQ_Q2pfvMK4XFG3RIOcUgMTlCny6dd0MMC-uLSQhx7rwZXPDFEApTTN1i-evHz5u188WlczH40_q8rs-Km7VtnU0n6KAzfbLvnvZjdPf56nYyLWfXX-rJeFa2HENVAiiqKtwZC6qDRhjBRSUkKOgIF6IyEgwTDYF2TlpuWwVKsgZb3GDKQVb0GF3sdNebZmXnrfVDNL1eR7cy8VEH4_S_N94t9SI86IoQySqWBc52AssXbdPxTG9rmArGsz0PJLOnT8Ni-LaxadArl1rb98bbsEkaBMvWM0xlRj--QO_DJvpsRaYEk5xRth0-2lFtDClF2-1fQLDepqi3Kep9irnhw9_f3ePPsWWg2gHfXW8f_yOnx1_rqz_ivwHIa6ZI</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2664754344</pqid></control><display><type>article</type><title>Dinitrogen Coordination to a High‐Spin Diiron(I/II) Species</title><source>MEDLINE</source><source>Wiley Online Library Journals Frontfile Complete</source><creator>Torres, Juan F. ; Oi, Collin H. ; Moseley, Ian P. ; El‐Sakkout, Nabila ; Knight, Brian J. ; Shearer, Jason ; García‐Serres, Ricardo ; Zadrozny, Joseph M. ; Murray, Leslie J.</creator><creatorcontrib>Torres, Juan F. ; Oi, Collin H. ; Moseley, Ian P. ; El‐Sakkout, Nabila ; Knight, Brian J. ; Shearer, Jason ; García‐Serres, Ricardo ; Zadrozny, Joseph M. ; Murray, Leslie J.</creatorcontrib><description>Dinitrogen coordination to iron centers underpins industrial and biological fixation in the Haber–Bosch process and by the FeM cofactors in the nitrogenase enzymes. The latter employ local high‐spin metal centers; however, iron–dinitrogen coordination chemistry remains dominated by low‐valent states, contrasting the enzyme systems. Here, we report a high‐spin mixed‐valent cis‐(μ‐1,2‐dinitrogen)diiron(I/II) complex [(FeBr)2(μ‐N2)Lbis]− (2), where [Lbis]− is a bis(β‐diketiminate) cyclophane. Field‐applied Mössbauer spectra, dc and ac magnetic susceptibility measurements, and computational methods support a delocalized S=7/2 Fe2N2 unit with D=−5.23 cm−1 and consequent slow magnetic relaxation.
Dinitrogen coordination to multiiron complexes is instrumental in understanding the reactivity of nitrogenases cofactors. The synthesis of a high‐spin mixed‐valent cis‐(μ‐1,2‐dinitrogen)diiron(I/II) complex obtained by a one‐electron reduction of a diiron(II/II) precursor is reported. The electronic structure of the complex was studied using Mössbauer spectroscopy, SQUID magnetometry, and DFT calculations, which support a S=7/2 ground state.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.202202329</identifier><identifier>PMID: 35302701</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>Chemical Sciences ; Cofactors ; Computer applications ; Coordination ; Coordination chemistry ; Cyclophane ; Electronic Structure ; Haber Bosch process ; Iron ; Magnetic induction ; Magnetic permeability ; Magnetic relaxation ; Magnetic susceptibility ; Mixed-Valent Compounds ; Mossbauer spectroscopy ; Multiiron Complexes ; Nitrogen Fixation ; Nitrogenase ; Physics ; Quantum Physics</subject><ispartof>Angewandte Chemie International Edition, 2022-05, Vol.61 (22), p.e202202329-n/a</ispartof><rights>2022 Wiley‐VCH GmbH</rights><rights>2022 Wiley-VCH GmbH.</rights><rights>Distributed under a Creative Commons Attribution 4.0 International License</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c5029-2283890fae28f2b6a656967282f15669a72a46b12cd1c5ec82874b0e0b0352793</citedby><cites>FETCH-LOGICAL-c5029-2283890fae28f2b6a656967282f15669a72a46b12cd1c5ec82874b0e0b0352793</cites><orcidid>0000-0002-1568-958X</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.202202329$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.202202329$$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/35302701$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://hal.science/hal-03645288$$DView record in HAL$$Hfree_for_read</backlink></links><search><creatorcontrib>Torres, Juan F.</creatorcontrib><creatorcontrib>Oi, Collin H.</creatorcontrib><creatorcontrib>Moseley, Ian P.</creatorcontrib><creatorcontrib>El‐Sakkout, Nabila</creatorcontrib><creatorcontrib>Knight, Brian J.</creatorcontrib><creatorcontrib>Shearer, Jason</creatorcontrib><creatorcontrib>García‐Serres, Ricardo</creatorcontrib><creatorcontrib>Zadrozny, Joseph M.</creatorcontrib><creatorcontrib>Murray, Leslie J.</creatorcontrib><title>Dinitrogen Coordination to a High‐Spin Diiron(I/II) Species</title><title>Angewandte Chemie International Edition</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>Dinitrogen coordination to iron centers underpins industrial and biological fixation in the Haber–Bosch process and by the FeM cofactors in the nitrogenase enzymes. The latter employ local high‐spin metal centers; however, iron–dinitrogen coordination chemistry remains dominated by low‐valent states, contrasting the enzyme systems. Here, we report a high‐spin mixed‐valent cis‐(μ‐1,2‐dinitrogen)diiron(I/II) complex [(FeBr)2(μ‐N2)Lbis]− (2), where [Lbis]− is a bis(β‐diketiminate) cyclophane. Field‐applied Mössbauer spectra, dc and ac magnetic susceptibility measurements, and computational methods support a delocalized S=7/2 Fe2N2 unit with D=−5.23 cm−1 and consequent slow magnetic relaxation.
Dinitrogen coordination to multiiron complexes is instrumental in understanding the reactivity of nitrogenases cofactors. The synthesis of a high‐spin mixed‐valent cis‐(μ‐1,2‐dinitrogen)diiron(I/II) complex obtained by a one‐electron reduction of a diiron(II/II) precursor is reported. The electronic structure of the complex was studied using Mössbauer spectroscopy, SQUID magnetometry, and DFT calculations, which support a S=7/2 ground state.</description><subject>Chemical Sciences</subject><subject>Cofactors</subject><subject>Computer applications</subject><subject>Coordination</subject><subject>Coordination chemistry</subject><subject>Cyclophane</subject><subject>Electronic Structure</subject><subject>Haber Bosch process</subject><subject>Iron</subject><subject>Magnetic induction</subject><subject>Magnetic permeability</subject><subject>Magnetic relaxation</subject><subject>Magnetic susceptibility</subject><subject>Mixed-Valent Compounds</subject><subject>Mossbauer spectroscopy</subject><subject>Multiiron Complexes</subject><subject>Nitrogen Fixation</subject><subject>Nitrogenase</subject><subject>Physics</subject><subject>Quantum Physics</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2022</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNqFkc1uEzEUhS1ERUvLliUaiU27mNS-_p0FlaK0kJEiumi7tjwTT-JqYgd7UtQdj8Az8iQ4ShugGyRLtq6_e659DkLvCR4RjOHceGdHgCEvCtUrdEQ4kJJKSV_nM6O0lIqTQ_Q2pfvMK4XFG3RIOcUgMTlCny6dd0MMC-uLSQhx7rwZXPDFEApTTN1i-evHz5u188WlczH40_q8rs-Km7VtnU0n6KAzfbLvnvZjdPf56nYyLWfXX-rJeFa2HENVAiiqKtwZC6qDRhjBRSUkKOgIF6IyEgwTDYF2TlpuWwVKsgZb3GDKQVb0GF3sdNebZmXnrfVDNL1eR7cy8VEH4_S_N94t9SI86IoQySqWBc52AssXbdPxTG9rmArGsz0PJLOnT8Ni-LaxadArl1rb98bbsEkaBMvWM0xlRj--QO_DJvpsRaYEk5xRth0-2lFtDClF2-1fQLDepqi3Kep9irnhw9_f3ePPsWWg2gHfXW8f_yOnx1_rqz_ivwHIa6ZI</recordid><startdate>20220523</startdate><enddate>20220523</enddate><creator>Torres, Juan F.</creator><creator>Oi, Collin H.</creator><creator>Moseley, Ian P.</creator><creator>El‐Sakkout, Nabila</creator><creator>Knight, Brian J.</creator><creator>Shearer, Jason</creator><creator>García‐Serres, Ricardo</creator><creator>Zadrozny, Joseph M.</creator><creator>Murray, Leslie J.</creator><general>Wiley Subscription Services, Inc</general><general>Wiley-VCH Verlag</general><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TM</scope><scope>K9.</scope><scope>7X8</scope><scope>1XC</scope><scope>VOOES</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0002-1568-958X</orcidid></search><sort><creationdate>20220523</creationdate><title>Dinitrogen Coordination to a High‐Spin Diiron(I/II) Species</title><author>Torres, Juan F. ; Oi, Collin H. ; Moseley, Ian P. ; El‐Sakkout, Nabila ; Knight, Brian J. ; Shearer, Jason ; García‐Serres, Ricardo ; Zadrozny, Joseph M. ; Murray, Leslie J.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c5029-2283890fae28f2b6a656967282f15669a72a46b12cd1c5ec82874b0e0b0352793</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2022</creationdate><topic>Chemical Sciences</topic><topic>Cofactors</topic><topic>Computer applications</topic><topic>Coordination</topic><topic>Coordination chemistry</topic><topic>Cyclophane</topic><topic>Electronic Structure</topic><topic>Haber Bosch process</topic><topic>Iron</topic><topic>Magnetic induction</topic><topic>Magnetic permeability</topic><topic>Magnetic relaxation</topic><topic>Magnetic susceptibility</topic><topic>Mixed-Valent Compounds</topic><topic>Mossbauer spectroscopy</topic><topic>Multiiron Complexes</topic><topic>Nitrogen Fixation</topic><topic>Nitrogenase</topic><topic>Physics</topic><topic>Quantum Physics</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Torres, Juan F.</creatorcontrib><creatorcontrib>Oi, Collin H.</creatorcontrib><creatorcontrib>Moseley, Ian P.</creatorcontrib><creatorcontrib>El‐Sakkout, Nabila</creatorcontrib><creatorcontrib>Knight, Brian J.</creatorcontrib><creatorcontrib>Shearer, Jason</creatorcontrib><creatorcontrib>García‐Serres, Ricardo</creatorcontrib><creatorcontrib>Zadrozny, Joseph M.</creatorcontrib><creatorcontrib>Murray, Leslie J.</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><collection>Hyper Article en Ligne (HAL)</collection><collection>Hyper Article en Ligne (HAL) (Open Access)</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Torres, Juan F.</au><au>Oi, Collin H.</au><au>Moseley, Ian P.</au><au>El‐Sakkout, Nabila</au><au>Knight, Brian J.</au><au>Shearer, Jason</au><au>García‐Serres, Ricardo</au><au>Zadrozny, Joseph M.</au><au>Murray, Leslie J.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Dinitrogen Coordination to a High‐Spin Diiron(I/II) Species</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2022-05-23</date><risdate>2022</risdate><volume>61</volume><issue>22</issue><spage>e202202329</spage><epage>n/a</epage><pages>e202202329-n/a</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>Dinitrogen coordination to iron centers underpins industrial and biological fixation in the Haber–Bosch process and by the FeM cofactors in the nitrogenase enzymes. The latter employ local high‐spin metal centers; however, iron–dinitrogen coordination chemistry remains dominated by low‐valent states, contrasting the enzyme systems. Here, we report a high‐spin mixed‐valent cis‐(μ‐1,2‐dinitrogen)diiron(I/II) complex [(FeBr)2(μ‐N2)Lbis]− (2), where [Lbis]− is a bis(β‐diketiminate) cyclophane. Field‐applied Mössbauer spectra, dc and ac magnetic susceptibility measurements, and computational methods support a delocalized S=7/2 Fe2N2 unit with D=−5.23 cm−1 and consequent slow magnetic relaxation.
Dinitrogen coordination to multiiron complexes is instrumental in understanding the reactivity of nitrogenases cofactors. The synthesis of a high‐spin mixed‐valent cis‐(μ‐1,2‐dinitrogen)diiron(I/II) complex obtained by a one‐electron reduction of a diiron(II/II) precursor is reported. The electronic structure of the complex was studied using Mössbauer spectroscopy, SQUID magnetometry, and DFT calculations, which support a S=7/2 ground state.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>35302701</pmid><doi>10.1002/anie.202202329</doi><tpages>4</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0002-1568-958X</orcidid><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1433-7851 |
| ispartof | Angewandte Chemie International Edition, 2022-05, Vol.61 (22), p.e202202329-n/a |
| issn | 1433-7851 1521-3773 |
| language | eng |
| recordid | cdi_pubmedcentral_primary_oai_pubmedcentral_nih_gov_9117494 |
| source | MEDLINE; Wiley Online Library Journals Frontfile Complete |
| subjects | Chemical Sciences Cofactors Computer applications Coordination Coordination chemistry Cyclophane Electronic Structure Haber Bosch process Iron Magnetic induction Magnetic permeability Magnetic relaxation Magnetic susceptibility Mixed-Valent Compounds Mossbauer spectroscopy Multiiron Complexes Nitrogen Fixation Nitrogenase Physics Quantum Physics |
| title | Dinitrogen Coordination to a High‐Spin Diiron(I/II) Species |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-02-13T06%3A20%3A54IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_pubme&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Dinitrogen%20Coordination%20to%20a%20High%E2%80%90Spin%20Diiron(I/II)%20Species&rft.jtitle=Angewandte%20Chemie%20International%20Edition&rft.au=Torres,%20Juan%20F.&rft.date=2022-05-23&rft.volume=61&rft.issue=22&rft.spage=e202202329&rft.epage=n/a&rft.pages=e202202329-n/a&rft.issn=1433-7851&rft.eissn=1521-3773&rft_id=info:doi/10.1002/anie.202202329&rft_dat=%3Cproquest_pubme%3E2641004037%3C/proquest_pubme%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=2664754344&rft_id=info:pmid/35302701&rfr_iscdi=true |