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  Electronic Structure of Mononuclear Bis(1,2-diaryl-1,2-ethylenedithiolato)iron Complexes Containing a Fifth Cyanide or Phosphite Ligand:  A Combined Experimental and Computational Study

Patra, A. K., Bill, E., Bothe, E., Chlopek, K., Neese, F., Weyhermüller, T., et al. (2006). Electronic Structure of Mononuclear Bis(1,2-diaryl-1,2-ethylenedithiolato)iron Complexes Containing a Fifth Cyanide or Phosphite Ligand:  A Combined Experimental and Computational Study. Inorganic Chemistry, 45(19), 7877-7890. doi:10.1021/ic061171t.

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Patra, Apurba K.1, Author              
Bill, Eckhard1, Author              
Bothe, Eberhard1, Author              
Chlopek, Krzysztof1, Author              
Neese, Frank1, Author              
Weyhermüller, Thomas1, Author              
Stobie, Keira2, Author
Ward, Michael D.3, Author
McCleverty, Jon A.2, Author
Wieghardt, Karl1, Author              
Affiliations:
1Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society, ou_3023881              
2School of Chemistry, University of Bristol, Bristol BS8 1TS, U.K., ou_persistent22              
3Department of Chemistry, University of Sheffield , Sheffield S3 7HF, U.K., ou_persistent22              

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 Abstract: A series of mononuclear square-based pyramidal complexes of iron containing two 1,2-diaryl-ethylene-1,2-dithiolate ligands in various oxidation levels has been synthesized. The reaction of the dinuclear species [FeIII2(1L)2(1L)2]0, where (1L)2- is the closed shell di-(4-tert-butylphenyl)-1,2-ethylenedithiolate dianion and (1L)1- is its one-electron-oxidized π-radical monoanion, with [N(n-Bu)4]CN in toluene yields dark green crystals of mononuclear [N(n-Bu)4][FeII(1L)2(CN)] (1). The oxidation of 1 with ferrocenium hexafluorophosphate yields blue [FeIII(1L)2(CN)] (1ox), and analogously, a reduction with [Cp2Co] yields [Cp2Co][N(n-Bu)4][FeII(1L)(1L)(CN)] (1red); oxidation of the neutral dimer with iodine gives [FeIII(1L)2I] (2). The dimer reacts with the phosphite P(OCH3)3 to yield [FeII(1L)2{P(OCH3)3}] (3), and [FeIII2(3L)2(3L)2] reacts with P(OC6H5)3 to give [FeII(3L)2{P(OC6H5)3}] (4), where (3L)2- represents 1,2-diphenyl-1,2-ethylenedithiolate(2−). Both 3 and 4 were electrochemically one-electron oxidized to the monocations 3ox and 4ox and reduced to the monoanions 3red and 4red. The structures of 1 and 4 have been determined by X-ray crystallography. All compounds have been studied by magnetic susceptibility measurements, X-band EPR, UV−vis, IR, and Mössbauer spectroscopies. The following five-coordinate chromophores have been identified:  (a) [FeIII(L)2X]n, X = CN-, I- (n = 0) (1ox, 2); X = P(OR)3 (n = 1+) )3ox, 4ox) with St = 1/2, SFe = 3/2; (b) [FeII(L)2X]n, X = CN-, (n = 1−) (1); X = P(OR)3 (n = 0) (3, 4) with St = SFe = 0; (c) [FeII(L)(L)X]n ↔ [FeII(L)(L)X]n, X = CN- (n = 2−) (1red); X = P(OR)3 (n = 1−) (3red, 4red) with St = 1/2, SFe = 0 (or 1). Complex 1ox displays spin crossover behavior:  St = 1/2 ↔ St = 3/2 with intrinsic spin-state change SFe = 3/2 ↔ SFe = 5/2. The electronic structures of 1 and 1ox have been established by density functional theoretical calculations:  [FeII(1L)2(CN)]1- (SFe = 0, St = 0) and [FeIII(1L)2(CN)]0 (SFe = 3/2, St = 1/2).

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Language(s): eng - English
 Dates: 2006-06-272006-08-102006-09-01
 Publication Status: Published in print
 Pages: 14
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/ic061171t
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Title: Inorganic Chemistry
  Abbreviation : Inorg. Chem.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 45 (19) Sequence Number: - Start / End Page: 7877 - 7890 Identifier: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669