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
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 [Fe4...
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todo:paper_14779226_v45_n1_p361_Schuren2023-10-03T16:19:17Z 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 Schüren, A.O. Gramm, V.K. Dürr, M. Foi, A. Ivanović-Burmazović, I. Doctorovich, F. Ruschewitz, U. Klein, A. 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 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. Fil:Doctorovich, F. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_14779226_v45_n1_p361_Schuren |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
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 |
| spellingShingle |
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 Schüren, A.O. Gramm, V.K. Dürr, M. Foi, A. Ivanović-Burmazović, I. Doctorovich, F. Ruschewitz, U. Klein, A. 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 |
| topic_facet |
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 |
| description |
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. |
| format |
JOUR |
| author |
Schüren, A.O. Gramm, V.K. Dürr, M. Foi, A. Ivanović-Burmazović, I. Doctorovich, F. Ruschewitz, U. Klein, A. |
| author_facet |
Schüren, A.O. Gramm, V.K. Dürr, M. Foi, A. Ivanović-Burmazović, I. Doctorovich, F. Ruschewitz, U. Klein, A. |
| author_sort |
Schüren, A.O. |
| title |
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 |
| title_short |
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 |
| title_full |
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 |
| title_fullStr |
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 |
| title_full_unstemmed |
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 |
| title_sort |
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 |
| url |
http://hdl.handle.net/20.500.12110/paper_14779226_v45_n1_p361_Schuren |
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