Journal article
A stable aminyl radical metal complex.
- Büttner T Department of Chemistry and Applied Biosciences, ETH Hönggerberg, CH-8093 Zürich, Switzerland.
- Geier J
- Frison G
- Harmer J
- Calle C
- Schweiger A
- Schönberg H
- Grützmacher H
- 2005-01-18
Published in:
- Science (New York, N.Y.). - 2005
English
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.
- Language
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- English
- Open access status
- closed
- Identifiers
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- DOI 10.1126/science.1106070
- PMID 15653498
- Persistent URL
- https://folia.unifr.ch/global/documents/164013
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