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  The Electronic Structure of Iron Corroles: A Combined Experimental and Quantum Chemical Study

Ye, S., Tuttle, T., Bill, E., Simkhovich, L., Gross, Z., Thiel, W., et al. (2008). The Electronic Structure of Iron Corroles: A Combined Experimental and Quantum Chemical Study. Chemistry – A European Journal, 14(34), 10839-10851. doi:10.1002/chem.200801265.

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 Creators:
Ye, Shengfa1, Author              
Tuttle, Tell2, Author              
Bill, Eckhard3, Author              
Simkhovich, Liliya4, Author
Gross, Zeev4, Author
Thiel, Walter2, Author              
Neese, Frank1, 3, Author              
Affiliations:
1Lehrstuhl für Theoretische Chemie, Institut für Physikalische und Theoretische Chemie, Universität Bonn, Wegelerstrasse 12, D-53115 Bonn, Germany, ou_persistent22              
2Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445590              
3Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society, ou_3023881              
4Schulich Faculty of Chemistry, Technion—Israel Institute of Technology, Haifa 32000 (Israel), ou_persistent22              

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Free keywords: corroles; density functional calculations; iron; N ligands; non-innocent ligands
 Abstract: There is a longstanding debate in the literature on the electronic structure of chloroiron corroles, especially for those containing the highly electron‐withdrawing meso‐tris(pentafluorophenyl)corrole (TPFC) ligand. Two alternative electronic structures were proposed for this and the related [FeCl(tdcc)] (TDCC=meso‐tris(2,6‐dichlorophenyl)corrole) complex, namely a high‐valent ferryl species chelated by a trianionic corrolato ligand ([FeIV(Cor)3−]+) or an intermediate‐spin (IS) ferric ion that is antiferromagnetically coupled to a dianionic π‐radical corrole ([FeIII(Cor).2−]+) yielding an overall triplet ground state. Two series of corrole‐based iron complexes ([Fe(L)(Cor)], in which L=F, Cl, Br, I, and Cor=TPFC, TDCC) have been investigated by a combined experimental (Mössbauer spectroscopy) and computational (DFT) approach in order to differentiate between the two possible electronic‐structure descriptions. The experimentally calibrated conclusions were reached by a detailed analysis of the Kohn–Sham solutions, which successfully reproduce the experimental structures and spectroscopic parameters: the electronic structures of [Fe(L)(Cor)] (L=F, Cl, Br, I, Cor=TPFC, TDCC) are best formulated as ([IS‐FeIII(Cor).2−]+), similar to chloroiron corrole complexes containing electron‐rich corrole ligands. The antiferromagnetic pathway is composed of singly occupied Fe dz2 and corrole a2u‐like π orbitals, with coupling constants that exceed those of analogous porphyrin systems by a factor of 2–3. In the corroles, the combination of lower symmetry, extra negative charge, and smaller cavity size (relative to the porphyrins) leads to exceptionally strong iron–corrole σ bonds. Hence, the Fe dx2-y2-based molecular orbital is unavailable in the corrole complexes (contrary to the porphyrin case), and the local spin states are SFe=3/2 in the corroles versus SFe=5/2 in the porphyrins. The consequences of this qualitative difference are discussed for spin distributions and magnetic properties.

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Language(s): eng - English
 Dates: 2008-11-212008-11-26
 Publication Status: Published in print
 Pages: 13
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/chem.200801265
 Degree: -

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Title: Chemistry – A European Journal
  Other : Chem. – Eur. J.
  Other : Chem. Eur. J.
Source Genre: Journal
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Publ. Info: Weinheim : Wiley-VCH
Pages: - Volume / Issue: 14 (34) Sequence Number: - Start / End Page: 10839 - 10851 Identifier: ISSN: 0947-6539
CoNE: https://pure.mpg.de/cone/journals/resource/954926979058