Dioxygen reactivity of Cu(I) complexes supported by β-diketiminate ligands: Distinguishing between kinetic and thermodynamic control

INOR 101

Lyndal M. R. Hill, hill@chem.umn.edu and William B. Tolman, tolman@chem.umn.edu. Department of Chemistry, University of Minnesota, 207 Pleasant St SE, Minneapolis, MN 55455
Copper monooxygenases utilize dioxygen for substrate oxidation, with the structural characterization of a 1:1 Cu/O2 intermediate in PHM providing insight into the form of the activated species. Model systems involving Cu(I) complexes of β-diketiminate ligands produce oxygenated species for which the reaction product is dependent on the ligand substituents. Backbone substituents attenuate the donating ability of the ligand, while the inclusion of sterically bulky phenyl groups attached on the nitrogen donors has been critical in limiting the formation of binuclear Cu/O2 species. We present here an investigation into the influence of ligand design, through backbone and N-substituent variations, on the identity of the Cu/O2 core in the product/s.
 

Inorganic Modeling of Biological Systems
1:30 PM-5:10 PM, Sunday, August 19, 2007 BCEC -- 208, Oral

Division of Inorganic Chemistry

The 234th ACS National Meeting, Boston, MA, August 19-23, 2007