title: Hydrogen-Atom Transfer (HAT) Initiated by Intramolecular Ligand-Metal Electron Transfer.
abstract: Hydrogen-atom transfer (HAT) is of key importance for several catalytic and biological processes, and provides an elegant access to C-H activation. In synthetic chemistry, a photoactivated metal complex is often employed to abstract an oxygen- or nitrogen-bound hydrogen, and the as-generated oxygen- or nitrogen-centered radical is the hydrogen-atom acceptor for HAT. Here, we report the first examples for HAT processes initiated by one-electron oxidation of urea azines. A further novelty is that the HAT-initiating oxidation can be realized by intramolecular ligand-metal electron transfer in copper(II)-urea azine complexes. These complexes are first characterized in the solid state, in which they are stable. Electron-transfer-initiated HAT processes are observed upon dissolving the complexes in organic solvents, and the kinetics of these processes varies with the solvent polarity. The carbon-centered radicals formed by HAT can either be trapped with 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) or undergo radical recombination reactions with itself, yielding diamagnetic end-products.
authors.affiliation: Anorganisch-Chemisches Institut, Ruprecht-Karls Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
authors.forename: Hendrik
authors.initials: H
authors.lastname: Herrmann
authors.affiliation: Anorganisch-Chemisches Institut, Ruprecht-Karls Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
authors.forename: Elisabeth
authors.initials: E
authors.lastname: Kaifer
authors.affiliation: Anorganisch-Chemisches Institut, Ruprecht-Karls Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
authors.forename: Hans-Jörg
authors.initials: HJ
authors.lastname: Himmel
keywords: coordination; electron transfer; hydrogen-atom transfer; organic electron donor; oxidation