Generation and substrate oxygenation reactions by an end-on bound Superoxo Copper(II) complex

INOR 102

Debabrata Maiti, dmaiti1@jhu.edu1, Harry C. Fry, fryhc@hotmail.com2, Julia S. Woertink, Julia.Woertink@stanford.edu3, Michael Vance3, E. I. Solomon3, and Kenneth D. Karlin, karlin@jhu.edu4. (1) Department of Chemistry, Johns Hopkins University, Baltimore, MD 21218, (2) Department of Chemistry, John Hopkins University, 3400 N. Charles Street, Baltimore, MD 21218, (3) Department of Chemistry, Stanford University, 333 Campus Drive, Mudd Building, Stanford, CA 94305, (4) Department of Chemistry, The Johns Hopkins University, 3400 N. Charles St., Baltimore, MD 21218
Employing a strongly electron-donating tripodal tetradentate ligand an end-on bound superoxo-copper(II) complex (CuII(O2–))has been generated. Resonance Raman spectroscopy employing isotopically substituted dioxygen (including mixed isotope 16/18O2) proves the end-on superoxo CuII(O2–) structural formulation. The first demonstration of CuII(O2–) oxidative reactivity studies with exogenous substrates, likely involving H-atom abstraction chemistry, comes with the finding that CuII(O2–) effects the oxygenation and hydroperoxylation of substituted phenols and substrate C-H activation.
 

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