A stable aminyl radical metal complex.

Journal article

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.

Authors: Büttner, T; Geier, J; Frison, G; Harmer, J; Calle, C

• Publication status: Published
• Journal: Science (New York, N.Y.)
• Volume: 307
• Issue: 5707
• Pages: 235-238
• Publication date: 2005-01-01
• DOI: 10.1126/science.1106070
• EISSN: 1095-9203
• ISSN: 0036-8075
• Language: English