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  Electronic Structures of Five‐Coordinate Complexes of Iron Containing Zero, One, or Two π‐Radical Ligands: A Broken‐Symmetry Density Functional Theoretical Study

Chlopek, K., Muresan, N., Neese, F., & Wieghardt, K. (2007). Electronic Structures of Five‐Coordinate Complexes of Iron Containing Zero, One, or Two π‐Radical Ligands: A Broken‐Symmetry Density Functional Theoretical Study. Chemistry – A European Journal, 13(30), 8390-8403. doi:10.1002/chem.200700897.

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 Creators:
Chlopek, Krzysztof1, Author              
Muresan, Nicoleta1, Author              
Neese, Frank2, Author              
Wieghardt, Karl1, Author              
Affiliations:
1Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society, ou_3023881              
2Lehrstuhl für Theoretische Chemie, Institut für Physikalische und Theoretische Chemie, Universität Bonn, Wegelerstrasse 12, D-53115 Bonn, Germany, ou_persistent22              

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Free keywords: density functional calculations; intermediate spin; iron; ligand effects; radicals
 Abstract: The electronic structures of a series of five‐coordinate complexes of iron containing zero, one, or two bidentate, organic π‐radical ligands and a monodentate ligand (pyridine, iodide) have been studied by broken‐symmetry (BS) density functional theoretical (DFT) methods. By analyzing the set of corresponding orbitals5 (CO) a convenient division of the spin‐up and spin‐down orbitals into 1) essentially doubly‐occupied molecular orbitals (MO), 2) exactly singly‐occupied MOs, 3) spin‐coupled pairs, and 4) virtual orbitals can be achieved and a clear picture of the spin coupling between the ligands (non‐innocence vs. innocence) and the central metal ion (dN configuration) can be generated. We have identified three classes of complexes which all contain a ferric ion (d5) with an intrinsic intermediate spin (SFe= 3/2) that yield 1) an St=3/2 ground spin state if the two bidentate ligands are closed‐shell species (innocent ligands); 2) if one π‐radical ligand is present, an St=1 ground state is obtained through intramolecular antiferromagnetic coupling; 3) if two such radicals are present, an St=1/2 ground state is obtained. We show unambiguously for the first time that the pentane‐2,4‐dione‐bis(S‐alkylisothiosemicarbazonato) ligand can bind as π‐radical dianion (L.TSC)2− in [FeIII(L.TSC)I] (St=1) (6); the description as [FeIV(LTSC3−)I] is incorrect. Similarly, the diamagnetic monoanion in 14 must be described as [FeIII(CN)2(L.TSC)] (St=0) with a low‐spin ferric ion (d5, SFe=1/2) coupled antiferromagnetically to a π‐radical ligand; [FeII(CN)2(LTSC)] is an incorrect description.

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Language(s): eng - English
 Dates: 2007-06-132007-10-022007-10-15
 Publication Status: Published in print
 Pages: 14
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/chem.200700897
 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: 13 (30) Sequence Number: - Start / End Page: 8390 - 8403 Identifier: ISSN: 0947-6539
CoNE: https://pure.mpg.de/cone/journals/resource/954926979058