Schueren, Andreas O., Gramm, Verena K., Duerr, Maximilian, Foi, Ana, Ivanovic-Burmazovic, Ivana, Doctorovich, Fabio, Ruschewitz, Uwe ORCID: 0000-0002-6511-6894 and Klein, Axel ORCID: 0000-0003-0093-9619 (2016). Halide coordinated homoleptic [Fe4S4X4](2-) and heteroleptic [Fe4S4X2Y2](2-) clusters (X, Y = Cl, Br, I)-alternative preparations, structural analogies and spectroscopic properties in solution and solid state. Dalton Trans., 45 (1). S. 361 - 376. CAMBRIDGE: ROYAL SOC CHEMISTRY. ISSN 1477-9234

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Abstract

New facile methods to prepare iron sulphur halide clusters [Fe4S4X4](2-) from [Fe(CO)(5)] and elemental sulphur were elaborated. Reactions of ferrous precursors like tetrahalidoferrates(II) or simple ferrous halides with [Fe(CO)(5)] and sulphur turned out to be efficient methods to prepare homoleptic [Fe4S4X4](2-) (X = Cl, Br) and heteroleptic clusters [Fe4S4X4-nYn](2-) (X = Cl, Br; Y = Br, I). Solid materials were obtained as salts of BTMA(+) (= benzyltrimethylammonium); the new compounds containing [Fe4S4Br4](2-) and [Fe4S4X2Y2](2-) (X, Y = Cl, Br, I) were all isostructural to (BTMA)(2)[Fe4S4I4] (monoclinic, Cc) as inferred from synchrotron X-ray powder diffraction. While the solid materials contain defined heteroleptic clusters with a halide X : Y ratio of 2 : 2, dissolving these compounds leads to rapid scrambling of the halide ligands forming mixtures of all five possible [Fe4S4X4-nYn](2-) clusters as could be shown by UHR-ESI MS. The variation of X and Y allowed assignment of the absorption bands in the visible and NIR; the long-wavelength bands around 1100 nm were tentatively assigned to intervalence charge transfer (IVCT) transitions.

Item Type: Journal Article
Creators:
CreatorsEmailORCIDORCID Put Code
Schueren, Andreas O.UNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Gramm, Verena K.UNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Duerr, MaximilianUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Foi, AnaUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Ivanovic-Burmazovic, IvanaUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Doctorovich, FabioUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Ruschewitz, UweUNSPECIFIEDorcid.org/0000-0002-6511-6894UNSPECIFIED
Klein, AxelUNSPECIFIEDorcid.org/0000-0003-0093-9619UNSPECIFIED
URN: urn:nbn:de:hbz:38-292131
DOI: 10.1039/c5dt02769a
Journal or Publication Title: Dalton Trans.
Volume: 45
Number: 1
Page Range: S. 361 - 376
Date: 2016
Publisher: ROYAL SOC CHEMISTRY
Place of Publication: CAMBRIDGE
ISSN: 1477-9234
Language: English
Faculty: Unspecified
Divisions: Unspecified
Subjects: no entry
Uncontrolled Keywords:
KeywordsLanguage
IRON-SULFUR CLUSTERS; SULFIDE-THIOLATE DIMERS; CHARGE-TRANSFER IVCT; CRYSTAL-STRUCTURES; 4FE-4S CLUSTERS; ACTIVE-SITES; CUBANE-TYPE; ELECTRONIC-STRUCTURE; INORGANIC DERIVATIVES; BIOMIMETIC CHALCOGELSMultiple languages
Chemistry, Inorganic & NuclearMultiple languages
Refereed: Yes
URI: http://kups.ub.uni-koeln.de/id/eprint/29213

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