Stable Aminyl Radical Metal Complex
Metal-stabilized phenoxyl radicals appear to be important intermediates in a variety of enzymatic oxidations. We report that transition metal coordination also supports an aminyl radical, resulting in a stable crystalline complex: [Rh(I)(trop₂N[superscript .])(bipy)]⁺OTf⁻ (where trop is 5-H-dibenzo[...
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| Veröffentlicht in: | Science (American Association for the Advancement of Science) 2005-01, Vol.307 (5707), p.235-238 |
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| creator | Bůttner, Torsten Geier, Jens Frison, Gilles Harmer, Jeffrey Calle, Carlos Schweiger, Arthur Schönberg, Hartmut Grůtzmacher, Hansjörg |
| description | Metal-stabilized phenoxyl radicals appear to be important intermediates in a variety of enzymatic oxidations. We report that transition metal coordination also supports an aminyl radical, resulting in a stable crystalline complex: [Rh(I)(trop₂N[superscript .])(bipy)]⁺OTf⁻ (where trop is 5-H-dibenzo[a,d]cycloheptene-5-yl, bipy is 2,2'-bipyridyl, OTf⁻ is trifluorosulfonate). It is accessible under mild conditions by one-electron oxidation of the amide complex [Rh(I)(trop₂N)(bipy)], at a potential of -0.55 volt versus ferrocene/ferrocenium. Both electron paramagnetic resonance spectroscopy and density functional theory support 57% localization of the unpaired spin at N. In reactions with H-atom donors, the Rh-coordinated aminyl behaves as a nucleophilic radical. |
| doi_str_mv | 10.1126/science.1106070 |
| format | Article |
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We report that transition metal coordination also supports an aminyl radical, resulting in a stable crystalline complex: [Rh(I)(trop₂N[superscript .])(bipy)]⁺OTf⁻ (where trop is 5-H-dibenzo[a,d]cycloheptene-5-yl, bipy is 2,2'-bipyridyl, OTf⁻ is trifluorosulfonate). It is accessible under mild conditions by one-electron oxidation of the amide complex [Rh(I)(trop₂N)(bipy)], at a potential of -0.55 volt versus ferrocene/ferrocenium. Both electron paramagnetic resonance spectroscopy and density functional theory support 57% localization of the unpaired spin at N. In reactions with H-atom donors, the Rh-coordinated aminyl behaves as a nucleophilic radical.</description><identifier>ISSN: 0036-8075</identifier><identifier>EISSN: 1095-9203</identifier><identifier>DOI: 10.1126/science.1106070</identifier><identifier>PMID: 15653498</identifier><identifier>CODEN: SCIEAS</identifier><language>eng</language><publisher>Washington, DC: American Association for the Advancement of Science</publisher><subject>Amides ; Amines ; Atoms ; Chemical reactions ; Chemical Sciences ; Chemistry ; Coordination chemistry ; Coordination compounds ; Degassing of metals ; Electrons ; Enzymes ; Exact sciences and technology ; Fullerenes ; Hydrogen ; Inorganic chemistry and origins of life ; Metals ; Metals (Materials) ; Molecular orbitals ; Molecular structure ; Nitrogen ; or physical chemistry ; Orbitals ; Oxidation ; Preparations and properties ; Theoretical and</subject><ispartof>Science (American Association for the Advancement of Science), 2005-01, Vol.307 (5707), p.235-238</ispartof><rights>Copyright 2005 American Association for the Advancement of Science</rights><rights>2005 INIST-CNRS</rights><rights>COPYRIGHT 2005 American Association for the Advancement of Science</rights><rights>COPYRIGHT 2005 American Association for the Advancement of Science</rights><rights>Copyright American Association for the Advancement of Science Jan 14, 2005</rights><rights>Distributed under a Creative Commons Attribution 4.0 International License</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c841t-b01cf6938132da9531b745fd60cc3fe0f0d35663d45bcd60b118f992a817db2b3</citedby><cites>FETCH-LOGICAL-c841t-b01cf6938132da9531b745fd60cc3fe0f0d35663d45bcd60b118f992a817db2b3</cites><orcidid>0000-0002-5677-3569</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://www.jstor.org/stable/pdf/3840104$$EPDF$$P50$$Gjstor$$H</linktopdf><linktohtml>$$Uhttps://www.jstor.org/stable/3840104$$EHTML$$P50$$Gjstor$$H</linktohtml><link.rule.ids>230,314,776,780,799,881,2871,2872,27901,27902,57992,58225</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=16432864$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/15653498$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://hal.science/hal-00466464$$DView record in HAL$$Hfree_for_read</backlink></links><search><creatorcontrib>Bůttner, Torsten</creatorcontrib><creatorcontrib>Geier, Jens</creatorcontrib><creatorcontrib>Frison, Gilles</creatorcontrib><creatorcontrib>Harmer, Jeffrey</creatorcontrib><creatorcontrib>Calle, Carlos</creatorcontrib><creatorcontrib>Schweiger, Arthur</creatorcontrib><creatorcontrib>Schönberg, Hartmut</creatorcontrib><creatorcontrib>Grůtzmacher, Hansjörg</creatorcontrib><title>Stable Aminyl Radical Metal Complex</title><title>Science (American Association for the Advancement of Science)</title><addtitle>Science</addtitle><description>Metal-stabilized phenoxyl radicals appear to be important intermediates in a variety of enzymatic oxidations. We report that transition metal coordination also supports an aminyl radical, resulting in a stable crystalline complex: [Rh(I)(trop₂N[superscript .])(bipy)]⁺OTf⁻ (where trop is 5-H-dibenzo[a,d]cycloheptene-5-yl, bipy is 2,2'-bipyridyl, OTf⁻ is trifluorosulfonate). It is accessible under mild conditions by one-electron oxidation of the amide complex [Rh(I)(trop₂N)(bipy)], at a potential of -0.55 volt versus ferrocene/ferrocenium. Both electron paramagnetic resonance spectroscopy and density functional theory support 57% localization of the unpaired spin at N. 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We report that transition metal coordination also supports an aminyl radical, resulting in a stable crystalline complex: [Rh(I)(trop₂N[superscript .])(bipy)]⁺OTf⁻ (where trop is 5-H-dibenzo[a,d]cycloheptene-5-yl, bipy is 2,2'-bipyridyl, OTf⁻ is trifluorosulfonate). It is accessible under mild conditions by one-electron oxidation of the amide complex [Rh(I)(trop₂N)(bipy)], at a potential of -0.55 volt versus ferrocene/ferrocenium. Both electron paramagnetic resonance spectroscopy and density functional theory support 57% localization of the unpaired spin at N. In reactions with H-atom donors, the Rh-coordinated aminyl behaves as a nucleophilic radical.</abstract><cop>Washington, DC</cop><pub>American Association for the Advancement of Science</pub><pmid>15653498</pmid><doi>10.1126/science.1106070</doi><tpages>4</tpages><orcidid>https://orcid.org/0000-0002-5677-3569</orcidid></addata></record> |
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| source | American Association for the Advancement of Science; Jstor Complete Legacy |
| subjects | Amides Amines Atoms Chemical reactions Chemical Sciences Chemistry Coordination chemistry Coordination compounds Degassing of metals Electrons Enzymes Exact sciences and technology Fullerenes Hydrogen Inorganic chemistry and origins of life Metals Metals (Materials) Molecular orbitals Molecular structure Nitrogen or physical chemistry Orbitals Oxidation Preparations and properties Theoretical and |
| title | Stable Aminyl Radical Metal Complex |
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