Electronic tuning of ß-diketiminate ligands with fluorinated substituents: Effects on the O2-reactivity of mononuclear Cu(I) complexes

INOR 938

Lyndal M. R. Hill, hill@chem.umn.edu, Benjamin F. Gherman, Nermeen W. Aboelella, Christopher J. Cramer, cramer@pollux.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 copper monooxygenases undergo dioxygen activation at a mononuclear copper site, for subsequent substrate oxidation. To date, there are few well-characterized synthetic examples of 1:1 Cu/O2 adducts, with all exhibiting side-on bonding of the O2 ligand. We present here the comparison of a ß-diketiminate ligand with fluorinated variants in the study of Cu(I)-O2 reactivity. The energetics of the oxygenation reactions of the Cu(I) complexes have been assessed by theory and the results compared with those obtained by experiment. The alterations made to the electronic environment of the ß-diketiminate ligand were probed by examining vibrational and electrochemical properties of the Cu(I) complexes. The complexes thus provide a useful series for gaining insights into the key determinants in Cu/O2 adduct formation for this class of ligand.
 

Bioinorganic Modeling
1:30 PM-5:30 PM, Wednesday, 13 September 2006 Moscone Center -- Room 307, Oral

Division of Inorganic Chemistry

The 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006