Heteroleptic and Homoleptic Iron(III) Complexes with a Tris(N‐Heterocyclic Carbene) Borate Ligand: Synthesis, Characterization, and Catalytic Application
Heteroleptic and homoleptic iron(III) complexes supported by a tris(N‐heterocyclic carbene) borate ligand have been prepared and crystallographically characterized. The strong electron‐donating character of the tris(carbene) donor was revealed by UV‐vis absorption spectroscopy and electrochemical me...
Gespeichert in:
Veröffentlicht in: | European journal of inorganic chemistry 2023-05, Vol.26 (14), p.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 | 14 |
container_start_page | |
container_title | European journal of inorganic chemistry |
container_volume | 26 |
creator | Sato, Yuna Okamura, Masaya Hikichi, Shiro |
description | Heteroleptic and homoleptic iron(III) complexes supported by a tris(N‐heterocyclic carbene) borate ligand have been prepared and crystallographically characterized. The strong electron‐donating character of the tris(carbene) donor was revealed by UV‐vis absorption spectroscopy and electrochemical measurements combined with quantum chemical calculations. The catalytic activity of each complex was evaluated in cyclohexane oxidation reaction using meta‐chloroperoxybenzoic acid (=mCPBA) as an oxidant, and both complexes show high catalytic activity and selectivity with TON=∼350 and A/(K+L)=8–10. Mechanistic studies suggested that radical‐chain processes are involved in the reaction due to mCPBA acting as a one‐electron oxidant, concomitant with the pathway of metal‐based reactive species. Moreover, it was found that the homoleptic and heteroleptic complexes differed significantly in the involvement of metal‐based active species, with the homoleptic complex exhibiting more metal‐based reactions.
Heteroleptic and homoleptic iron(III) complexes with tris(N‐heterocyclic carbene) borate ligands were synthesized and fully characterized. Both complexes showed high catalytic activity and alcohol selectivity in the cyclohexane oxidation reaction. Mechanistic investigation revealed that the catalysis of the homoleptic complex involves more metal‐based active species. |
doi_str_mv | 10.1002/ejic.202200728 |
format | Article |
fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_journals_2812886825</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2812886825</sourcerecordid><originalsourceid>FETCH-LOGICAL-c3578-44bac509f95a7dac556ea92aff15853670be967c87b99347ac40ec1e13eecc203</originalsourceid><addsrcrecordid>eNqFkTtPwzAUhSMEEs-V2RILSE25dl42G0RAgyoYgDlyzQ11lcbBDoIw8RPY-Xf8ElzKY2S698rnO0fyCYJdCkMKwA5xptWQAWMAGeMrwQYFIUJIOVv1exzFIRUxXw82nZsBQARRuhG8j7BDa2psO62IbO7IyMx_zsKaZr8oigOSm3lb4zM68qS7KZHkxmq3f_nx-rbkVa9qD-TSTrDBA3JirOyQjPW9tzwi133TTdFpNyD5VFqpPKNfZKdNM_gKzWUn636Redy23unraTtYq2TtcOd7bgW3Z6c3-SgcX50X-fE4VFGS8TCOJ1IlICqRyOzOr0mKUjBZVTThSZRmMEGRZopnEyGiOJMqBlQUaYSoFINoK9hb-rbWPDyi68qZebSNjywZp4xz_4WJVw2XKmWNcxarsrV6Lm1fUigXBZSLAsrfAjwglsCTrrH_R12eXhT5H_sJCsqMwA</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2812886825</pqid></control><display><type>article</type><title>Heteroleptic and Homoleptic Iron(III) Complexes with a Tris(N‐Heterocyclic Carbene) Borate Ligand: Synthesis, Characterization, and Catalytic Application</title><source>Access via Wiley Online Library</source><creator>Sato, Yuna ; Okamura, Masaya ; Hikichi, Shiro</creator><creatorcontrib>Sato, Yuna ; Okamura, Masaya ; Hikichi, Shiro</creatorcontrib><description>Heteroleptic and homoleptic iron(III) complexes supported by a tris(N‐heterocyclic carbene) borate ligand have been prepared and crystallographically characterized. The strong electron‐donating character of the tris(carbene) donor was revealed by UV‐vis absorption spectroscopy and electrochemical measurements combined with quantum chemical calculations. The catalytic activity of each complex was evaluated in cyclohexane oxidation reaction using meta‐chloroperoxybenzoic acid (=mCPBA) as an oxidant, and both complexes show high catalytic activity and selectivity with TON=∼350 and A/(K+L)=8–10. Mechanistic studies suggested that radical‐chain processes are involved in the reaction due to mCPBA acting as a one‐electron oxidant, concomitant with the pathway of metal‐based reactive species. Moreover, it was found that the homoleptic and heteroleptic complexes differed significantly in the involvement of metal‐based active species, with the homoleptic complex exhibiting more metal‐based reactions.
Heteroleptic and homoleptic iron(III) complexes with tris(N‐heterocyclic carbene) borate ligands were synthesized and fully characterized. Both complexes showed high catalytic activity and alcohol selectivity in the cyclohexane oxidation reaction. Mechanistic investigation revealed that the catalysis of the homoleptic complex involves more metal‐based active species.</description><identifier>ISSN: 1434-1948</identifier><identifier>EISSN: 1099-0682</identifier><identifier>DOI: 10.1002/ejic.202200728</identifier><language>eng</language><publisher>Weinheim: Wiley Subscription Services, Inc</publisher><subject>Absorption spectroscopy ; alkanes ; carbene ligands ; Carbenes ; Catalytic activity ; Chemical synthesis ; Crystallography ; Cyclohexane ; homogeneous catalysis ; Inorganic chemistry ; Iron ; Ligands ; Oxidation ; Oxidizing agents ; Quantum chemistry</subject><ispartof>European journal of inorganic chemistry, 2023-05, Vol.26 (14), p.n/a</ispartof><rights>2023 The Authors. European Journal of Inorganic Chemistry 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-c3578-44bac509f95a7dac556ea92aff15853670be967c87b99347ac40ec1e13eecc203</citedby><cites>FETCH-LOGICAL-c3578-44bac509f95a7dac556ea92aff15853670be967c87b99347ac40ec1e13eecc203</cites><orcidid>0000-0002-8899-5019 ; 0000-0001-6001-9780</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%2Fejic.202200728$$EPDF$$P50$$Gwiley$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fejic.202200728$$EHTML$$P50$$Gwiley$$Hfree_for_read</linktohtml><link.rule.ids>314,780,784,1417,27924,27925,45574,45575</link.rule.ids></links><search><creatorcontrib>Sato, Yuna</creatorcontrib><creatorcontrib>Okamura, Masaya</creatorcontrib><creatorcontrib>Hikichi, Shiro</creatorcontrib><title>Heteroleptic and Homoleptic Iron(III) Complexes with a Tris(N‐Heterocyclic Carbene) Borate Ligand: Synthesis, Characterization, and Catalytic Application</title><title>European journal of inorganic chemistry</title><description>Heteroleptic and homoleptic iron(III) complexes supported by a tris(N‐heterocyclic carbene) borate ligand have been prepared and crystallographically characterized. The strong electron‐donating character of the tris(carbene) donor was revealed by UV‐vis absorption spectroscopy and electrochemical measurements combined with quantum chemical calculations. The catalytic activity of each complex was evaluated in cyclohexane oxidation reaction using meta‐chloroperoxybenzoic acid (=mCPBA) as an oxidant, and both complexes show high catalytic activity and selectivity with TON=∼350 and A/(K+L)=8–10. Mechanistic studies suggested that radical‐chain processes are involved in the reaction due to mCPBA acting as a one‐electron oxidant, concomitant with the pathway of metal‐based reactive species. Moreover, it was found that the homoleptic and heteroleptic complexes differed significantly in the involvement of metal‐based active species, with the homoleptic complex exhibiting more metal‐based reactions.
Heteroleptic and homoleptic iron(III) complexes with tris(N‐heterocyclic carbene) borate ligands were synthesized and fully characterized. Both complexes showed high catalytic activity and alcohol selectivity in the cyclohexane oxidation reaction. Mechanistic investigation revealed that the catalysis of the homoleptic complex involves more metal‐based active species.</description><subject>Absorption spectroscopy</subject><subject>alkanes</subject><subject>carbene ligands</subject><subject>Carbenes</subject><subject>Catalytic activity</subject><subject>Chemical synthesis</subject><subject>Crystallography</subject><subject>Cyclohexane</subject><subject>homogeneous catalysis</subject><subject>Inorganic chemistry</subject><subject>Iron</subject><subject>Ligands</subject><subject>Oxidation</subject><subject>Oxidizing agents</subject><subject>Quantum chemistry</subject><issn>1434-1948</issn><issn>1099-0682</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><sourceid>24P</sourceid><sourceid>WIN</sourceid><recordid>eNqFkTtPwzAUhSMEEs-V2RILSE25dl42G0RAgyoYgDlyzQ11lcbBDoIw8RPY-Xf8ElzKY2S698rnO0fyCYJdCkMKwA5xptWQAWMAGeMrwQYFIUJIOVv1exzFIRUxXw82nZsBQARRuhG8j7BDa2psO62IbO7IyMx_zsKaZr8oigOSm3lb4zM68qS7KZHkxmq3f_nx-rbkVa9qD-TSTrDBA3JirOyQjPW9tzwi133TTdFpNyD5VFqpPKNfZKdNM_gKzWUn636Redy23unraTtYq2TtcOd7bgW3Z6c3-SgcX50X-fE4VFGS8TCOJ1IlICqRyOzOr0mKUjBZVTThSZRmMEGRZopnEyGiOJMqBlQUaYSoFINoK9hb-rbWPDyi68qZebSNjywZp4xz_4WJVw2XKmWNcxarsrV6Lm1fUigXBZSLAsrfAjwglsCTrrH_R12eXhT5H_sJCsqMwA</recordid><startdate>20230512</startdate><enddate>20230512</enddate><creator>Sato, Yuna</creator><creator>Okamura, Masaya</creator><creator>Hikichi, Shiro</creator><general>Wiley Subscription Services, Inc</general><scope>24P</scope><scope>WIN</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><orcidid>https://orcid.org/0000-0002-8899-5019</orcidid><orcidid>https://orcid.org/0000-0001-6001-9780</orcidid></search><sort><creationdate>20230512</creationdate><title>Heteroleptic and Homoleptic Iron(III) Complexes with a Tris(N‐Heterocyclic Carbene) Borate Ligand: Synthesis, Characterization, and Catalytic Application</title><author>Sato, Yuna ; Okamura, Masaya ; Hikichi, Shiro</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c3578-44bac509f95a7dac556ea92aff15853670be967c87b99347ac40ec1e13eecc203</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><topic>Absorption spectroscopy</topic><topic>alkanes</topic><topic>carbene ligands</topic><topic>Carbenes</topic><topic>Catalytic activity</topic><topic>Chemical synthesis</topic><topic>Crystallography</topic><topic>Cyclohexane</topic><topic>homogeneous catalysis</topic><topic>Inorganic chemistry</topic><topic>Iron</topic><topic>Ligands</topic><topic>Oxidation</topic><topic>Oxidizing agents</topic><topic>Quantum chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Sato, Yuna</creatorcontrib><creatorcontrib>Okamura, Masaya</creatorcontrib><creatorcontrib>Hikichi, Shiro</creatorcontrib><collection>Wiley Online Library Open Access</collection><collection>Wiley Online Library (Open Access Collection)</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><jtitle>European journal of inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Sato, Yuna</au><au>Okamura, Masaya</au><au>Hikichi, Shiro</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Heteroleptic and Homoleptic Iron(III) Complexes with a Tris(N‐Heterocyclic Carbene) Borate Ligand: Synthesis, Characterization, and Catalytic Application</atitle><jtitle>European journal of inorganic chemistry</jtitle><date>2023-05-12</date><risdate>2023</risdate><volume>26</volume><issue>14</issue><epage>n/a</epage><issn>1434-1948</issn><eissn>1099-0682</eissn><abstract>Heteroleptic and homoleptic iron(III) complexes supported by a tris(N‐heterocyclic carbene) borate ligand have been prepared and crystallographically characterized. The strong electron‐donating character of the tris(carbene) donor was revealed by UV‐vis absorption spectroscopy and electrochemical measurements combined with quantum chemical calculations. The catalytic activity of each complex was evaluated in cyclohexane oxidation reaction using meta‐chloroperoxybenzoic acid (=mCPBA) as an oxidant, and both complexes show high catalytic activity and selectivity with TON=∼350 and A/(K+L)=8–10. Mechanistic studies suggested that radical‐chain processes are involved in the reaction due to mCPBA acting as a one‐electron oxidant, concomitant with the pathway of metal‐based reactive species. Moreover, it was found that the homoleptic and heteroleptic complexes differed significantly in the involvement of metal‐based active species, with the homoleptic complex exhibiting more metal‐based reactions.
Heteroleptic and homoleptic iron(III) complexes with tris(N‐heterocyclic carbene) borate ligands were synthesized and fully characterized. Both complexes showed high catalytic activity and alcohol selectivity in the cyclohexane oxidation reaction. Mechanistic investigation revealed that the catalysis of the homoleptic complex involves more metal‐based active species.</abstract><cop>Weinheim</cop><pub>Wiley Subscription Services, Inc</pub><doi>10.1002/ejic.202200728</doi><tpages>9</tpages><orcidid>https://orcid.org/0000-0002-8899-5019</orcidid><orcidid>https://orcid.org/0000-0001-6001-9780</orcidid><oa>free_for_read</oa></addata></record> |
fulltext | fulltext |
identifier | ISSN: 1434-1948 |
ispartof | European journal of inorganic chemistry, 2023-05, Vol.26 (14), p.n/a |
issn | 1434-1948 1099-0682 |
language | eng |
recordid | cdi_proquest_journals_2812886825 |
source | Access via Wiley Online Library |
subjects | Absorption spectroscopy alkanes carbene ligands Carbenes Catalytic activity Chemical synthesis Crystallography Cyclohexane homogeneous catalysis Inorganic chemistry Iron Ligands Oxidation Oxidizing agents Quantum chemistry |
title | Heteroleptic and Homoleptic Iron(III) Complexes with a Tris(N‐Heterocyclic Carbene) Borate Ligand: Synthesis, Characterization, and Catalytic Application |
url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-23T09%3A28%3A43IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Heteroleptic%20and%20Homoleptic%20Iron(III)%20Complexes%20with%20a%20Tris(N%E2%80%90Heterocyclic%20Carbene)%20Borate%20Ligand:%20Synthesis,%20Characterization,%20and%20Catalytic%20Application&rft.jtitle=European%20journal%20of%20inorganic%20chemistry&rft.au=Sato,%20Yuna&rft.date=2023-05-12&rft.volume=26&rft.issue=14&rft.epage=n/a&rft.issn=1434-1948&rft.eissn=1099-0682&rft_id=info:doi/10.1002/ejic.202200728&rft_dat=%3Cproquest_cross%3E2812886825%3C/proquest_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=2812886825&rft_id=info:pmid/&rfr_iscdi=true |