Intramolecular Redox-Active Ligand-to-Substrate Single-Electron Transfer: Radical Reactivity with a Palladium(II) Complex
Journal of the American Chemical Society2014Vol. 136(33), pp. 11574–11577
Citations Over TimeTop 10% of 2014 papers
Daniël L. J. Broere, Bas de Bruin, Joost N. H. Reek, Martin Lutz, Sebastian Dechert, Jarl Ivar van der Vlugt
Abstract
Coordination of the redox-active tridentate NNO ligand L(H2) to Pd(II) yields the paramagnetic iminobenzosemiquinonato complex 3. Single-electron reduction of 3 yields diamagnetic amidophenolato complex 4, capable of activating aliphatic azide 5. Experimental and computational studies suggest a redox-noninnocent pathway wherein the redox-active ligand facilitates intramolecular ligand-to-substrate single-electron transfer to generate an open-shell singlet "nitrene-substrate radical, ligand radical", enabling subsequent radical-type C-H amination reactivity with Pd(II).
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