Get access

Benzylic Ligand Hydroxylation Starting from a Dicopper μ-η22 Peroxo Intermediate: Dramatic Acceleration of the Reaction by Hydrogen-Atom Donors

Authors

  • Dr. Malte Rolff,

    1. Institut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Strasse 2, 24118 Kiel (Germany), Fax: (+49) 431-880-1520
    Search for more papers by this author
  • Jessica Nadine Hamann,

    1. Institut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Strasse 2, 24118 Kiel (Germany), Fax: (+49) 431-880-1520
    Search for more papers by this author
  • Prof. Dr. Felix Tuczek

    Corresponding author
    1. Institut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Strasse 2, 24118 Kiel (Germany), Fax: (+49) 431-880-1520
    • Institut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Strasse 2, 24118 Kiel (Germany), Fax: (+49) 431-880-1520
    Search for more papers by this author

  • The authors acknowledge synthetic and spectroscopic support by Ursula Cornelissen, Stephanie Pehlke, Marianne Karbstein, Dr. Gerhardt Peters, and Madleen Sallmann.

Abstract

original image

Radicals in directed pathways: The μ-η22 peroxo CuII2 intermediate 1 shows a much faster benzylic ligand hydroxylation than systems without phenol. This novel reactivity can be further accelerated by addition of external H-atom donors such as TEMPO-H. The results imply initial H-atom transfer leading to the formation of phenoxyl radicals. A highly reactive copper oxyl intermediate is then formed, which inserts oxygen into the benzylic C[BOND]H bond.

Ancillary