Modeling TauD‑ J : A High-Spin Nonheme Oxoiron(IV) Complex with High Reactivity toward C–H Bonds
High-spin oxoiron(IV) species are often implicated in the mechanisms of nonheme iron oxygenases, their C–H bond cleaving properties being attributed to the quintet spin state. However, the few available synthetic S = 2 FeIVO complexes supported by polydentate ligands do not cleave strong C–H bonds....
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| Veröffentlicht in: | Journal of the American Chemical Society 2015-02, Vol.137 (7), p.2428-2431 |
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| container_title | Journal of the American Chemical Society |
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| creator | Biswas, Achintesh N Puri, Mayank Meier, Katlyn K Oloo, Williamson N Rohde, Gregory T Bominaar, Emile L Münck, Eckard Que, Lawrence |
| description | High-spin oxoiron(IV) species are often implicated in the mechanisms of nonheme iron oxygenases, their C–H bond cleaving properties being attributed to the quintet spin state. However, the few available synthetic S = 2 FeIVO complexes supported by polydentate ligands do not cleave strong C–H bonds. Herein we report the characterization of a highly reactive S = 2 complex, [FeIV(O)(TQA)(NCMe)]2+ (2) (TQA = tris(2-quinolylmethyl)amine), which oxidizes both C–H and CC bonds at −40 °C. The oxidation of cyclohexane by 2 occurs at a rate comparable to that of the oxidation of taurine by the TauD- J enzyme intermediate after adjustment for the different temperatures of measurement. Moreover, compared with other S = 2 complexes characterized to date, the spectroscopic properties of 2 most closely resemble those of TauD- J . Together these features make 2 the best electronic and functional model for TauD- J to date. |
| doi_str_mv | 10.1021/ja511757j |
| format | Article |
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Together these features make 2 the best electronic and functional model for TauD- J to date.</description><subject>Biomimetic Materials - chemistry</subject><subject>Carbon - chemistry</subject><subject>Hydrogen - chemistry</subject><subject>Iron - chemistry</subject><subject>Mixed Function Oxygenases - metabolism</subject><subject>Models, Molecular</subject><subject>Molecular Conformation</subject><subject>Organometallic Compounds - chemistry</subject><subject>Oxidation-Reduction</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2015</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNpt0ElOwzAYBWALgWgpLLgA8gYJFgEPsZ2yK2FoEYPEtI1c22ldJXGJE9ruegXEDTkJgQIrVr9-6dOT3gNgF6MjjAg-nkiGsWBisgbamBEUMEz4OmgjhEggIk5bYMv7SfOGJMKboEUYFyHnpA30jdMms8UIPsr67GP5Bq_gCezBvh2Ng4epLeCtK8YmN_Bu7mzpioPB8yGMXT7NzBzObDX-pvDeSFXZV1stYOVmstQw_li-9-GpK7TfBhupzLzZ-bkd8HRx_hj3g-u7y0Hcuw4kxawKRBcNecSo4VilNIy4MhENh0R3jWaEaUWpQhEVrKtTI1POhoYKyQVLRShDrGgHHKxyp6V7qY2vktx6ZbJMFsbVPsGcRQIxSmhDD1dUlc770qTJtLS5LBcJRsnXqMnfqI3d-4mth7nRf_J3xQbsr4BUPpm4uiyalv8EfQJ_On1J</recordid><startdate>20150225</startdate><enddate>20150225</enddate><creator>Biswas, Achintesh N</creator><creator>Puri, Mayank</creator><creator>Meier, Katlyn K</creator><creator>Oloo, Williamson N</creator><creator>Rohde, Gregory T</creator><creator>Bominaar, Emile L</creator><creator>Münck, Eckard</creator><creator>Que, Lawrence</creator><general>American Chemical Society</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>7X8</scope></search><sort><creationdate>20150225</creationdate><title>Modeling TauD‑ J : A High-Spin Nonheme Oxoiron(IV) Complex with High Reactivity toward C–H Bonds</title><author>Biswas, Achintesh N ; Puri, Mayank ; Meier, Katlyn K ; Oloo, Williamson N ; Rohde, Gregory T ; Bominaar, Emile L ; Münck, Eckard ; Que, Lawrence</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a315t-790b6853e61cf3486ce834b2d9ed525dc33c083759dfeaf65be37a675f74a41c3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2015</creationdate><topic>Biomimetic Materials - chemistry</topic><topic>Carbon - chemistry</topic><topic>Hydrogen - chemistry</topic><topic>Iron - chemistry</topic><topic>Mixed Function Oxygenases - metabolism</topic><topic>Models, Molecular</topic><topic>Molecular Conformation</topic><topic>Organometallic Compounds - chemistry</topic><topic>Oxidation-Reduction</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Biswas, Achintesh N</creatorcontrib><creatorcontrib>Puri, Mayank</creatorcontrib><creatorcontrib>Meier, Katlyn K</creatorcontrib><creatorcontrib>Oloo, Williamson N</creatorcontrib><creatorcontrib>Rohde, Gregory T</creatorcontrib><creatorcontrib>Bominaar, Emile L</creatorcontrib><creatorcontrib>Münck, Eckard</creatorcontrib><creatorcontrib>Que, Lawrence</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Biswas, Achintesh N</au><au>Puri, Mayank</au><au>Meier, Katlyn K</au><au>Oloo, Williamson N</au><au>Rohde, Gregory T</au><au>Bominaar, Emile L</au><au>Münck, Eckard</au><au>Que, Lawrence</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Modeling TauD‑ J : A High-Spin Nonheme Oxoiron(IV) Complex with High Reactivity toward C–H Bonds</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2015-02-25</date><risdate>2015</risdate><volume>137</volume><issue>7</issue><spage>2428</spage><epage>2431</epage><pages>2428-2431</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>High-spin oxoiron(IV) species are often implicated in the mechanisms of nonheme iron oxygenases, their C–H bond cleaving properties being attributed to the quintet spin state. However, the few available synthetic S = 2 FeIVO complexes supported by polydentate ligands do not cleave strong C–H bonds. Herein we report the characterization of a highly reactive S = 2 complex, [FeIV(O)(TQA)(NCMe)]2+ (2) (TQA = tris(2-quinolylmethyl)amine), which oxidizes both C–H and CC bonds at −40 °C. The oxidation of cyclohexane by 2 occurs at a rate comparable to that of the oxidation of taurine by the TauD- J enzyme intermediate after adjustment for the different temperatures of measurement. Moreover, compared with other S = 2 complexes characterized to date, the spectroscopic properties of 2 most closely resemble those of TauD- J . Together these features make 2 the best electronic and functional model for TauD- J to date.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>25674662</pmid><doi>10.1021/ja511757j</doi><tpages>4</tpages></addata></record> |
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| subjects | Biomimetic Materials - chemistry Carbon - chemistry Hydrogen - chemistry Iron - chemistry Mixed Function Oxygenases - metabolism Models, Molecular Molecular Conformation Organometallic Compounds - chemistry Oxidation-Reduction |
| title | Modeling TauD‑ J : A High-Spin Nonheme Oxoiron(IV) Complex with High Reactivity toward C–H Bonds |
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