Universität zu Köln

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:	Creators Email ORCID ORCID Put Code Schueren, Andreas O. UNSPECIFIED UNSPECIFIED UNSPECIFIED Gramm, Verena K. UNSPECIFIED UNSPECIFIED UNSPECIFIED Duerr, Maximilian UNSPECIFIED UNSPECIFIED UNSPECIFIED Foi, Ana UNSPECIFIED UNSPECIFIED UNSPECIFIED Ivanovic-Burmazovic, Ivana UNSPECIFIED UNSPECIFIED UNSPECIFIED Doctorovich, Fabio UNSPECIFIED UNSPECIFIED UNSPECIFIED Ruschewitz, Uwe UNSPECIFIED orcid.org/0000-0002-6511-6894 UNSPECIFIED Klein, Axel UNSPECIFIED orcid.org/0000-0003-0093-9619 UNSPECIFIED
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:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Inorganic Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language IRON-SULFUR CLUSTERS; SULFIDE-THIOLATE DIMERS; CHARGE-TRANSFER IVCT; CRYSTAL-STRUCTURES; 4FE-4S CLUSTERS; ACTIVE-SITES; CUBANE-TYPE; ELECTRONIC-STRUCTURE; INORGANIC DERIVATIVES; BIOMIMETIC CHALCOGELS Multiple languages Chemistry, Inorganic & Nuclear Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/29213