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Iron L-edge X-ray A...
Iron L-edge X-ray Absorption Spectroscopy of Oxy-Picket Fence Porphyrin : Electronic Structure of the Fe-O2 Bond
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- Wilson, Samuel (author)
- Stanford Univ, Dept Chem, Stanford, CA 94305 USA
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- Kroll, Thomas (author)
- Stanford Univ, Dept Chem, Stanford, CA 94305 USA
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- Decreau, Richard (author)
- Stanford Univ, Dept Chem, Stanford, CA 94305 USA
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- Hocking, Rosalie (author)
- Stanford Univ, Dept Chem, Stanford, CA 94305 USA
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- Lundberg, Marcus, 1974- (author)
- Stanford Univ, Dept Chem, Stanford, CA 94305 USA
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- Hedman, Britt (author)
- Stanford Univ, SLAC Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Menlo Pk, CA 94025 USA
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- Hodgson, Keith (author)
- Stanford Univ, Dept Chem, Stanford, CA 94305 USA; Stanford Univ, SLAC Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Menlo Pk, CA 94025 USA
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- Solomon, Edward (author)
- Stanford Univ, Dept Chem, Stanford, CA 94305 USA; Stanford Univ, SLAC Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Menlo Pk, CA 94025 USA
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(creator_code:org_t)
- 2013-01-10
- 2013
- English.
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In: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 135:3, s. 1124-1136
- Related links:
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https://uu.diva-port... (primary) (Raw object)
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https://europepmc.or...
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https://urn.kb.se/re...
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https://doi.org/10.1...
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Abstract
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- The electronic structure of the Fe-O-2 center in oxy-hemoglobin and oxy-myoglobin is a long-standing issue in the field of bioinorganic chemistry. Spectroscopic studies have been complicated by the highly delocalized nature of the porphyrin, and calculations require interpretation of multi-determinant wave functions for a highly covalent metal site. Here, iron L-edge X-ray absorption spectroscopy, interpreted using a valence bond configuration interaction multiplet model, is applied to directly probe the electronic structure of the iron in the biomimetic Fe-O-2 heme complex [Fe(pfp)-(1-Melm)O-2] (pfp ("picket fence porphyrin") = meso-tetra(alpha,alpha,alpha,alpha-o-pivalamidophenyl)porphyrin or TpivPP). This method allows separate estimates of sigma-donor, pi-donor, and pi-acceptor interactions through ligand-to-metal charge transfer and metal-to-ligand charge transfer mixing pathways. The L-edge spectrum of [Fe(pfp)(1-MeIm)O-2] is further compared to those of [Fe-II(pfp)(1-MeIm)(2)], [Fe-II(pfp)], and [Fe-III(tpp)(ImH)(2)]Cl (tpp = meso-tetraphenylporphyrin) which have Fe-II S = 0, Fe-II S = 1, and Fe-III S = 1/2 ground states, respectively. These serve as references for the three possible contributions to the ground state of oxy-pfp. The Fe-O-2 pfp site is experimentally determined to have both significant sigma-donation and a strong pi-interaction of the O-2 with the iron, with the latter having implications with respect to the spin polarization of the ground state.
Subject headings
- NATURVETENSKAP -- Kemi -- Fysikalisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Physical Chemistry (hsv//eng)
Keyword
- Chemistry
- Kemi
Publication and Content Type
- ref (subject category)
- art (subject category)
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