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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. © The Royal Society of Chemistry.

Registro:

Documento: Artículo
Título: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
Autor:Schüren, A.O.; Gramm, V.K.; Dürr, M.; Foi, A.; Ivanović-Burmazović, I.; Doctorovich, F.; Ruschewitz, U.; Klein, A.
Filiación:Department für Chemie, Institut für Anorganische Chemie, Universität zu Köln, Greinstraße 6, Köln, 50939, Germany
Departamento de Química Inorgánica, Analítica, y Química Física, Facultad de Ciencias Exactas y Naturales, INQUIMAE, CONICET, Universidad de Buenos Aires, Ciudad Universitaria Pabellón 2 Piso 3, Buenos Aires, C1428EHA, Argentina
Department Chemie und Pharmazie, Lehrstuhl für Bioanorgansiche Chemie, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 1, Erlangen, 91058, Germany
Palabras clave:Bromine compounds; Charge transfer; Chlorine compounds; Iron; Sulfur; X ray powder diffraction; Benzyltrimethylammonium; Elemental sulphur; Halide clusters; Intervalence charge transfer; Long wavelength bands; Spectroscopic property; Structural analogies; Synchrotron X ray powder diffraction; Iron compounds
Año:2015
Volumen:45
Número:1
Página de inicio:361
Página de fin:375
DOI: http://dx.doi.org/10.1039/c5dt02769a
Título revista:Dalton Transactions
Título revista abreviado:Dalton Trans.
ISSN:14779226
CODEN:DTARA
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14779226_v45_n1_p361_Schuren

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Citas:

---------- APA ----------
Schüren, A.O., Gramm, V.K., Dürr, M., Foi, A., Ivanović-Burmazović, I., Doctorovich, F., Ruschewitz, U.,..., Klein, A. (2015) . 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 Transactions, 45(1), 361-375.
http://dx.doi.org/10.1039/c5dt02769a
---------- CHICAGO ----------
Schüren, A.O., Gramm, V.K., Dürr, M., Foi, A., Ivanović-Burmazović, I., Doctorovich, F., et al. "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 Transactions 45, no. 1 (2015) : 361-375.
http://dx.doi.org/10.1039/c5dt02769a
---------- MLA ----------
Schüren, A.O., Gramm, V.K., Dürr, M., Foi, A., Ivanović-Burmazović, I., Doctorovich, F., et al. "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 Transactions, vol. 45, no. 1, 2015, pp. 361-375.
http://dx.doi.org/10.1039/c5dt02769a
---------- VANCOUVER ----------
Schüren, A.O., Gramm, V.K., Dürr, M., Foi, A., Ivanović-Burmazović, I., Doctorovich, F., et al. 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. 2015;45(1):361-375.
http://dx.doi.org/10.1039/c5dt02769a