The structures of the solvated iron(II) and iron(III) ions have been studied in solution and solid state by extended X-ray absorption fine structure (EXAFS) in three oxygen donor solvents, water, dimethylsulfoxide (Me2SO), N,N'-dimethylpropyleneurea (DMPU), and one sulfur donor solvent, N,N-dimethylthioformamide (DMTF); these solvents have different coordination and solvation properties. In addition, the structure of hexakis(dimethylsulfoxide)iron(III) perchlorate has been determined crystallographically to support the determination of the corresponding solvate in solution. The hydrated, the dimethylsulfoxide and N,N-dimethylthioformamide solvated iron(II) ions show regular octahedral coordination in both solution and solid state with mean Fe-O, Fe-O, and Fe-S bond distances of 2.10, 2.10, and 2.52 angstrom, respectively, whereas the N,N'-dimethylpropyleneurea iron(II) solvate is five-coordinated, d(Fe-O) = 2.06 angstrom. The compounds vary in color from light green (hydrate) to dark orange or red (DMPU). The hydrated iron(III) ion in aqueous solution and the dimethylsulfoxide solvated iron(III) ions in solution and solid state show the expected octahedral coordination, the Fe-O bond distances are 2.00 angstrom for both, whereas the N,N'-dimethylpropyleneurea iron(III) solvate is found to be five-coordinated with a mean Fe-O bond distance of 1.99 angstrom. The N,N-dimethylthioformamide solvated iron(III) ion in the solid perchlorate salt is tetrahedrally four-coordinated, the mean Fe-S bond distance is 2.20 angstrom. Iron(III) is reduced with time to iron(II) in N,N-dimethylthioformamide solution. The compounds vary in color from pale yellow (hydrate) to blackish red (DMPU). (C) 2006 Elsevier B.V. All rights reserved. Document Type: Article

A structural study of the hydrated and the dimethylsulfoxide, N,N'-dimethylpropyleneurea, N,N-dimethylthioformamide solvated iron(II) and iron(III) ions in solution and solid state / D., Lundberg; A. S., Ullstrm; D'Angelo, Paola; I., Persson. - In: INORGANICA CHIMICA ACTA. - ISSN 0020-1693. - STAMPA. - 360:(2007), pp. 1809-1818. [10.1016/j.ica.2006.09.014]

A structural study of the hydrated and the dimethylsulfoxide, N,N'-dimethylpropyleneurea, N,N-dimethylthioformamide solvated iron(II) and iron(III) ions in solution and solid state

D'ANGELO, Paola;
2007

Abstract

The structures of the solvated iron(II) and iron(III) ions have been studied in solution and solid state by extended X-ray absorption fine structure (EXAFS) in three oxygen donor solvents, water, dimethylsulfoxide (Me2SO), N,N'-dimethylpropyleneurea (DMPU), and one sulfur donor solvent, N,N-dimethylthioformamide (DMTF); these solvents have different coordination and solvation properties. In addition, the structure of hexakis(dimethylsulfoxide)iron(III) perchlorate has been determined crystallographically to support the determination of the corresponding solvate in solution. The hydrated, the dimethylsulfoxide and N,N-dimethylthioformamide solvated iron(II) ions show regular octahedral coordination in both solution and solid state with mean Fe-O, Fe-O, and Fe-S bond distances of 2.10, 2.10, and 2.52 angstrom, respectively, whereas the N,N'-dimethylpropyleneurea iron(II) solvate is five-coordinated, d(Fe-O) = 2.06 angstrom. The compounds vary in color from light green (hydrate) to dark orange or red (DMPU). The hydrated iron(III) ion in aqueous solution and the dimethylsulfoxide solvated iron(III) ions in solution and solid state show the expected octahedral coordination, the Fe-O bond distances are 2.00 angstrom for both, whereas the N,N'-dimethylpropyleneurea iron(III) solvate is found to be five-coordinated with a mean Fe-O bond distance of 1.99 angstrom. The N,N-dimethylthioformamide solvated iron(III) ion in the solid perchlorate salt is tetrahedrally four-coordinated, the mean Fe-S bond distance is 2.20 angstrom. Iron(III) is reduced with time to iron(II) in N,N-dimethylthioformamide solution. The compounds vary in color from pale yellow (hydrate) to blackish red (DMPU). (C) 2006 Elsevier B.V. All rights reserved. Document Type: Article
2007
01 Pubblicazione su rivista::01a Articolo in rivista
A structural study of the hydrated and the dimethylsulfoxide, N,N'-dimethylpropyleneurea, N,N-dimethylthioformamide solvated iron(II) and iron(III) ions in solution and solid state / D., Lundberg; A. S., Ullstrm; D'Angelo, Paola; I., Persson. - In: INORGANICA CHIMICA ACTA. - ISSN 0020-1693. - STAMPA. - 360:(2007), pp. 1809-1818. [10.1016/j.ica.2006.09.014]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/45336
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