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Iron L-edge X-ray A...
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Wilson, SamuelStanford Univ, Dept Chem, Stanford, CA 94305 USA
(författare)
Iron L-edge X-ray Absorption Spectroscopy of Oxy-Picket Fence Porphyrin : Electronic Structure of the Fe-O2 Bond
- Artikel/kapitelEngelska2013
Förlag, utgivningsår, omfång ...
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2013-01-10
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American Chemical Society (ACS),2013
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electronicrdacarrier
Nummerbeteckningar
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LIBRIS-ID:oai:DiVA.org:uu-198495
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https://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-198495URI
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https://doi.org/10.1021/ja3103583DOI
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Språk:engelska
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Sammanfattning på:engelska
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Ämneskategori:art swepub-publicationtype
Anmärkningar
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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.
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Biuppslag (personer, institutioner, konferenser, titlar ...)
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Kroll, ThomasStanford Univ, Dept Chem, Stanford, CA 94305 USA
(författare)
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Decreau, RichardStanford Univ, Dept Chem, Stanford, CA 94305 USA
(författare)
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Hocking, RosalieStanford Univ, Dept Chem, Stanford, CA 94305 USA
(författare)
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Lundberg, Marcus,1974-Stanford Univ, Dept Chem, Stanford, CA 94305 USA(Swepub:uu)marlu250
(författare)
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Hedman, BrittStanford Univ, SLAC Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Menlo Pk, CA 94025 USA
(författare)
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Hodgson, KeithStanford Univ, Dept Chem, Stanford, CA 94305 USA; Stanford Univ, SLAC Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Menlo Pk, CA 94025 USA
(författare)
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Solomon, EdwardStanford Univ, Dept Chem, Stanford, CA 94305 USA; Stanford Univ, SLAC Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Menlo Pk, CA 94025 USA
(författare)
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Stanford Univ, Dept Chem, Stanford, CA 94305 USAStanford Univ, SLAC Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Menlo Pk, CA 94025 USA
(creator_code:org_t)
Sammanhörande titlar
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Ingår i:Journal of the American Chemical Society: American Chemical Society (ACS)135:3, s. 1124-11360002-78631520-5126
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