title: Intramolecular redox-active ligand-to-substrate single-electron transfer: radical reactivity with a palladium(II) complex.
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).
authors.affiliation: Homogeneous, Bioinspired & Supramolecular Catalysis, van 't Hoff Institute for Molecular Sciences, University of Amsterdam , Science Park 904, 1098 XH Amsterdam, The Netherlands.
authors.forename: Daniël L J
authors.initials: DL
authors.lastname: Broere
authors.forename: Bas
authors.initials: B
authors.lastname: de Bruin
authors.forename: Joost N H
authors.initials: JN
authors.lastname: Reek
authors.forename: Martin
authors.initials: M
authors.lastname: Lutz
authors.forename: Sebastian
authors.initials: S
authors.lastname: Dechert
authors.forename: Jarl Ivar
authors.initials: JI
authors.lastname: van der Vlugt
mesh_terms: D004583:Electrons; D005609:Free Radicals / Q000737:chemistry; D008024:Ligands; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry*; D011789:Quantum Theory; D013237:Stereoisomerism
chemical_list: D005609:Free Radicals; D008024:Ligands; D009942:Organometallic Compounds; D010165:Palladium