A Stable Aminyl Radical Metal Complex

Abstract : 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.
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https://hal.archives-ouvertes.fr/hal-00466464
Contributeur : Gilles Frison <>
Soumis le : mardi 23 mars 2010 - 22:41:34
Dernière modification le : mardi 5 mars 2019 - 09:30:10

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Torsten Büttner, Jens Geier, Gilles Frison, Jeffrey Harmer, Carlos Calle, et al.. A Stable Aminyl Radical Metal Complex. Science, American Association for the Advancement of Science, 2005, 307, pp.235-238. ⟨10.1126/science.1106070⟩. ⟨hal-00466464⟩

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