Specific Enhancement of Catalytic Activity by a Dicopper Core: Selective Hydroxylation of Benzene to Phenol with Hydrogen Peroxide
A dicopper(II) complex, stabilized by the bis(tpa) ligand 1,2‐bis[2‐[bis(2‐pyridylmethyl)aminomethyl]‐6‐pyridyl]ethane (6‐hpa), [Cu2(μ‐OH)(6‐hpa)]3+, was synthesized and structurally characterized. This complex catalyzed selective hydroxylation of benzene to phenol using H2O2, thus attaining large t...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2017-06, Vol.56 (27), p.7779-7782 |
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| creator | Tsuji, Tomokazu Zaoputra, Antonius Andre Hitomi, Yutaka Mieda, Kaoru Ogura, Takashi Shiota, Yoshihito Yoshizawa, Kazunari Sato, Hiroyasu Kodera, Masahito |
| description | A dicopper(II) complex, stabilized by the bis(tpa) ligand 1,2‐bis[2‐[bis(2‐pyridylmethyl)aminomethyl]‐6‐pyridyl]ethane (6‐hpa), [Cu2(μ‐OH)(6‐hpa)]3+, was synthesized and structurally characterized. This complex catalyzed selective hydroxylation of benzene to phenol using H2O2, thus attaining large turnover numbers (TONs) and high H2O2 efficiency. The TON after 40 hours for the phenol production exceeded 12000 in MeCN at 50 °C under N2, the highest value reported for benzene hydroxylation with H2O2 catalyzed by homogeneous complexes. At 22 % benzene conversion, phenol (95.2 %) and p‐benzoquinone (4.8 %) were produced. The mechanism of H2O2 activation and benzene hydroxylation is proposed.
Doubled up: A new dicopper complex with a dinucleating ligand, which specifically stabilizes a dinuclear structure, displays enhanced catalytic activity, selectivity, and H2O2 efficiency in the selective hydroxylation of benzene to phenol using H2O2. The dinuclear structure is favorable for the formation of the active species that specifically enhance the catalytic activity. |
| doi_str_mv | 10.1002/anie.201702291 |
| format | Article |
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Doubled up: A new dicopper complex with a dinucleating ligand, which specifically stabilizes a dinuclear structure, displays enhanced catalytic activity, selectivity, and H2O2 efficiency in the selective hydroxylation of benzene to phenol using H2O2. The dinuclear structure is favorable for the formation of the active species that specifically enhance the catalytic activity.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.201702291</identifier><identifier>PMID: 28561921</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>arenes ; Benzene ; Benzoquinone ; Catalysis ; Catalytic activity ; Chemical synthesis ; copper ; Ethane ; Hydrocarbons ; Hydrogen peroxide ; Hydroxylation ; oxidation ; Phenols ; Quinones ; reaction mechanisms ; structure elucidation</subject><ispartof>Angewandte Chemie International Edition, 2017-06, Vol.56 (27), p.7779-7782</ispartof><rights>2017 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><rights>2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c4101-737b45524ec3632f2f9e2e2b9725851b75bc27a342b4aedd9428e7d51bba05733</citedby><cites>FETCH-LOGICAL-c4101-737b45524ec3632f2f9e2e2b9725851b75bc27a342b4aedd9428e7d51bba05733</cites><orcidid>0000-0001-9979-1743</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.201702291$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.201702291$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,780,784,1417,27924,27925,45574,45575</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/28561921$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Tsuji, Tomokazu</creatorcontrib><creatorcontrib>Zaoputra, Antonius Andre</creatorcontrib><creatorcontrib>Hitomi, Yutaka</creatorcontrib><creatorcontrib>Mieda, Kaoru</creatorcontrib><creatorcontrib>Ogura, Takashi</creatorcontrib><creatorcontrib>Shiota, Yoshihito</creatorcontrib><creatorcontrib>Yoshizawa, Kazunari</creatorcontrib><creatorcontrib>Sato, Hiroyasu</creatorcontrib><creatorcontrib>Kodera, Masahito</creatorcontrib><title>Specific Enhancement of Catalytic Activity by a Dicopper Core: Selective Hydroxylation of Benzene to Phenol with Hydrogen Peroxide</title><title>Angewandte Chemie International Edition</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>A dicopper(II) complex, stabilized by the bis(tpa) ligand 1,2‐bis[2‐[bis(2‐pyridylmethyl)aminomethyl]‐6‐pyridyl]ethane (6‐hpa), [Cu2(μ‐OH)(6‐hpa)]3+, was synthesized and structurally characterized. This complex catalyzed selective hydroxylation of benzene to phenol using H2O2, thus attaining large turnover numbers (TONs) and high H2O2 efficiency. The TON after 40 hours for the phenol production exceeded 12000 in MeCN at 50 °C under N2, the highest value reported for benzene hydroxylation with H2O2 catalyzed by homogeneous complexes. At 22 % benzene conversion, phenol (95.2 %) and p‐benzoquinone (4.8 %) were produced. The mechanism of H2O2 activation and benzene hydroxylation is proposed.
Doubled up: A new dicopper complex with a dinucleating ligand, which specifically stabilizes a dinuclear structure, displays enhanced catalytic activity, selectivity, and H2O2 efficiency in the selective hydroxylation of benzene to phenol using H2O2. The dinuclear structure is favorable for the formation of the active species that specifically enhance the catalytic activity.</description><subject>arenes</subject><subject>Benzene</subject><subject>Benzoquinone</subject><subject>Catalysis</subject><subject>Catalytic activity</subject><subject>Chemical synthesis</subject><subject>copper</subject><subject>Ethane</subject><subject>Hydrocarbons</subject><subject>Hydrogen peroxide</subject><subject>Hydroxylation</subject><subject>oxidation</subject><subject>Phenols</subject><subject>Quinones</subject><subject>reaction mechanisms</subject><subject>structure elucidation</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2017</creationdate><recordtype>article</recordtype><recordid>eNqF0c1vFCEYBnBiNLZWrx4NiRcvs8LLMAze1nVtmzTapHqeMMw7Ls0sjAxrHY_-5bLZfiReeoLk_fEEeAh5zdmCMwbvjXe4AMYVA9D8CTnmEnghlBJP874UolC15EfkxTRdZ1_XrHpOjqCWFdfAj8nfqxGt652la78x3uIWfaKhpyuTzDCnPFja5H65NNN2poZ-cjaMI0a6ChE_0CsccD9HejZ3MfyeB5Nc8PuEj-j_oEeaAr3coA8DvXFpc3A_0NNLzN51-JI8680w4avb9YR8_7z-tjorLr6enq-WF4UtOeOFEqotpYQSragE9NBrBIRWK5D5ia2SrQVlRAltabDrdAk1qi5PWsOkEuKEvDvkjjH83OGUmq2bLA6D8Rh2U8M1K0FwXUGmb_-j12EXfb5dVpxXWuafzGpxUDaGaYrYN2N0WxPnhrNm306zb6e5bycfeHMbu2u32N3zuzoy0Adw4wacH4lrll_O1w_h_wBno5vD</recordid><startdate>20170626</startdate><enddate>20170626</enddate><creator>Tsuji, Tomokazu</creator><creator>Zaoputra, Antonius Andre</creator><creator>Hitomi, Yutaka</creator><creator>Mieda, Kaoru</creator><creator>Ogura, Takashi</creator><creator>Shiota, Yoshihito</creator><creator>Yoshizawa, Kazunari</creator><creator>Sato, Hiroyasu</creator><creator>Kodera, Masahito</creator><general>Wiley Subscription Services, Inc</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TM</scope><scope>K9.</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0001-9979-1743</orcidid></search><sort><creationdate>20170626</creationdate><title>Specific Enhancement of Catalytic Activity by a Dicopper Core: Selective Hydroxylation of Benzene to Phenol with Hydrogen Peroxide</title><author>Tsuji, Tomokazu ; Zaoputra, Antonius Andre ; Hitomi, Yutaka ; Mieda, Kaoru ; Ogura, Takashi ; Shiota, Yoshihito ; Yoshizawa, Kazunari ; Sato, Hiroyasu ; Kodera, Masahito</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c4101-737b45524ec3632f2f9e2e2b9725851b75bc27a342b4aedd9428e7d51bba05733</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2017</creationdate><topic>arenes</topic><topic>Benzene</topic><topic>Benzoquinone</topic><topic>Catalysis</topic><topic>Catalytic activity</topic><topic>Chemical synthesis</topic><topic>copper</topic><topic>Ethane</topic><topic>Hydrocarbons</topic><topic>Hydrogen peroxide</topic><topic>Hydroxylation</topic><topic>oxidation</topic><topic>Phenols</topic><topic>Quinones</topic><topic>reaction mechanisms</topic><topic>structure elucidation</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Tsuji, Tomokazu</creatorcontrib><creatorcontrib>Zaoputra, Antonius Andre</creatorcontrib><creatorcontrib>Hitomi, Yutaka</creatorcontrib><creatorcontrib>Mieda, Kaoru</creatorcontrib><creatorcontrib>Ogura, Takashi</creatorcontrib><creatorcontrib>Shiota, Yoshihito</creatorcontrib><creatorcontrib>Yoshizawa, Kazunari</creatorcontrib><creatorcontrib>Sato, Hiroyasu</creatorcontrib><creatorcontrib>Kodera, Masahito</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Tsuji, Tomokazu</au><au>Zaoputra, Antonius Andre</au><au>Hitomi, Yutaka</au><au>Mieda, Kaoru</au><au>Ogura, Takashi</au><au>Shiota, Yoshihito</au><au>Yoshizawa, Kazunari</au><au>Sato, Hiroyasu</au><au>Kodera, Masahito</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Specific Enhancement of Catalytic Activity by a Dicopper Core: Selective Hydroxylation of Benzene to Phenol with Hydrogen Peroxide</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2017-06-26</date><risdate>2017</risdate><volume>56</volume><issue>27</issue><spage>7779</spage><epage>7782</epage><pages>7779-7782</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>A dicopper(II) complex, stabilized by the bis(tpa) ligand 1,2‐bis[2‐[bis(2‐pyridylmethyl)aminomethyl]‐6‐pyridyl]ethane (6‐hpa), [Cu2(μ‐OH)(6‐hpa)]3+, was synthesized and structurally characterized. This complex catalyzed selective hydroxylation of benzene to phenol using H2O2, thus attaining large turnover numbers (TONs) and high H2O2 efficiency. The TON after 40 hours for the phenol production exceeded 12000 in MeCN at 50 °C under N2, the highest value reported for benzene hydroxylation with H2O2 catalyzed by homogeneous complexes. At 22 % benzene conversion, phenol (95.2 %) and p‐benzoquinone (4.8 %) were produced. The mechanism of H2O2 activation and benzene hydroxylation is proposed.
Doubled up: A new dicopper complex with a dinucleating ligand, which specifically stabilizes a dinuclear structure, displays enhanced catalytic activity, selectivity, and H2O2 efficiency in the selective hydroxylation of benzene to phenol using H2O2. The dinuclear structure is favorable for the formation of the active species that specifically enhance the catalytic activity.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>28561921</pmid><doi>10.1002/anie.201702291</doi><tpages>4</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0001-9979-1743</orcidid></addata></record> |
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| subjects | arenes Benzene Benzoquinone Catalysis Catalytic activity Chemical synthesis copper Ethane Hydrocarbons Hydrogen peroxide Hydroxylation oxidation Phenols Quinones reaction mechanisms structure elucidation |
| title | Specific Enhancement of Catalytic Activity by a Dicopper Core: Selective Hydroxylation of Benzene to Phenol with Hydrogen Peroxide |
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