Affiliation:
1. Department of Chemistry and Applied Biosciences, ETH Hönggerberg, CH-8093 Zürich, Switzerland.
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)(trop
2
N
.
)(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)(trop
2
N)(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.
Publisher
American Association for the Advancement of Science (AAAS)
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