A stable aminyl radical metal complex

摘要: 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 stable crystalline complex: [Rh(I)(trop2N.)(bipy)]+OTf– (where trop is 5-H-dibenzo[a,d]cycloheptene-5-yl, bipy 2,2′-bipyridyl, OTf– trifluorosulfonate). It accessible under mild conditions by one-electron oxidation the amide complex [Rh(I)(trop2N)(bipy)], at potential –0.55 volt versus ferrocene/ferrocenium. Both electron paramagnetic resonance spectroscopy and density functional theory support 57% localization unpaired spin N. In reactions with H-atom donors, Rh-coordinated behaves as nucleophilic radical.