Novel reactivity of a μ-η22-disulfidodicopper complex supported by a neutral bidentate N-donor ligand

INOR 105

Itsik Bar-Nahum, barna048@umn.edu, John T. York, jyork@chem.umn.edu, and William B. Tolman, tolman@chem.umn.edu. Department of Chemistry, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455
The distinctive structure of the “CuZ” active site of the nitrous oxide reductase enzyme and the provocative hypothesis for the mechanism of its catalytic reactivity provide impetus for the study of synthetic model complexes. Towards this aim, we present the structural, electronic and spectroscopic characterization of a novel μ-η22 disulfidodicopper complex supported by a neutral bidentate N-donor ligand. The new Cu2S2 complex undergoes interesting 2H+ + 2e- oxidation processes (e.g., oxidation of 3,5-di-tert-butyl catechol or 2,4-di-tert-butyl phenol), S-atom transfer reactions, and S22- exchange reactions (e.g., formation of [Cu3S2]3+ cluster). These reactivities are not observed with other Cu2S2 complexes supported by neutral tridentate N-donor ligands and are distinguishable from the reactivity observed in the Cu2O2 analogs.