A 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.)(bipy)]+OTf- (where trop is 5-H-dibenzo[a,d]cyclohepte...
| Автори: | , , , , , , , |
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| Формат: | Journal article |
| Мова: | English |
| Опубліковано: |
2005
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| _version_ | 1826290822700597248 |
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| author | Büttner, T Geier, J Frison, G Harmer, J Calle, C Schweiger, A Schönberg, H Grützmacher, H |
| author_facet | Büttner, T Geier, J Frison, G Harmer, J Calle, C Schweiger, A Schönberg, H Grützmacher, H |
| author_sort | Büttner, T |
| collection | OXFORD |
| 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.)(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. |
| first_indexed | 2024-03-07T02:50:05Z |
| format | Journal article |
| id | oxford-uuid:ad62c8fe-01c4-40f8-a21e-84990bae34f1 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T02:50:05Z |
| publishDate | 2005 |
| record_format | dspace |
| spelling | oxford-uuid:ad62c8fe-01c4-40f8-a21e-84990bae34f12022-03-27T03:35:13ZA stable aminyl radical metal complex.Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:ad62c8fe-01c4-40f8-a21e-84990bae34f1EnglishSymplectic Elements at Oxford2005Büttner, TGeier, JFrison, GHarmer, JCalle, CSchweiger, ASchönberg, HGrützmacher, HMetal-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.)(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. |
| spellingShingle | Büttner, T Geier, J Frison, G Harmer, J Calle, C Schweiger, A Schönberg, H Grützmacher, H A stable aminyl radical metal complex. |
| title | A stable aminyl radical metal complex. |
| title_full | A stable aminyl radical metal complex. |
| title_fullStr | A stable aminyl radical metal complex. |
| title_full_unstemmed | A stable aminyl radical metal complex. |
| title_short | A stable aminyl radical metal complex. |
| title_sort | stable aminyl radical metal complex |
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