ISBN: 978-83-60043-10-3 - eurobic9

Eurobic9, 2-6 September, 2008, Wrocław, Poland
SL21. Insight into the Electronic Structure of ‘High-valent’ Iron
Complexes: Addressing Metal- vs Ligand-based Oxidations Using XAS and
TD-DFT
S. DeBeer George
SSRL, SLAC, Stanford University, 2575 Sand Hill Road, 94025, Menlo Park, United States,
e-mail: debeer@stanford.edu
Recently, we have used a combination of metal k-edge XAS combined with time-dependent density functional
theory, in order to probe the electronic structure of Fe(IV), Fe(V) and Fe(VI) complexes. This combination of
experimental data coupled to theory has also been extended to the controversial Fe(IV)-chloro-corrole
complexes. These complexes are formally Fe(IV), but may be described as either and S=1 Fe(IV) or an
intermediate spin Fe(III) antiferromagnetically coupled to a corrole radical. By using a combination of Fe K-, Cl
K- and N K-edges, the corrole complexes are compared to their porphyrin analogues in order to differentiate the
two possible corrole electronic structures. These results are coupled to TD-DFT. Implications for reactivity will
be discussed.
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