[Fe(4)S(4)](q) cubane clusters (q = 4+, 3+, 2+) with terminal amide ligands
| Autor: | Sonny C. Lee, Jeremiah S. Duncan, Christopher R Sharp |
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| Rok vydání: | 2010 |
| Předmět: |
Models
Molecular Magnetic Resonance Spectroscopy Trimethylsilyl Stereochemistry Iron chemistry.chemical_element Crystallography X-Ray Ligands Redox Inorganic Chemistry chemistry.chemical_compound X-Ray Diffraction Coordination Complexes Amide Molecule Physical and Theoretical Chemistry Molecular Structure Nuclear magnetic resonance spectroscopy Amides Crystallography chemistry Cubane X-ray crystallography Lithium Oxidation-Reduction Sulfur |
| Zdroj: | Inorganic chemistry. 49(14) |
| ISSN: | 1520-510X |
| Popis: | Bis(trimethylsilyl)amide-ligated iron-sulfur cubane clusters [Fe(4)(mu(3)-S)(4)(N{SiMe(3)}(2))(4)](z) (z = 0, 1-, 2-) are accessible by the reaction of FeCl(N{SiMe(3)}(2))(2)(THF) (1) with 1 equiv of NaSH (z = 0), followed by reduction with either 0.25 (z = 1-) or 1 equiv (z = 2-) of Na(2)S as needed. The anionic clusters are obtained as the sodium salts [Na(THF)(2)][Fe(4)S(4)(N{SiMe(3)}(2))(4)] and [Na(THF)(2)](2)[Fe(4)S(4)(N{SiMe(3)}(2))(4)]; in the solid state, these two clusters both possess a unique contact ion pair motif in which individual sodium ions each coordinate to a cluster core sulfide, an adjacent amide nitrogen, and two THF donors. The monoanionic cluster can also be prepared as the lithium salt [Li(THF)(4)][Fe(4)S(4)(N{SiMe(3)}(2))(4)] by the reaction of 1 with 1:0.5 LiCl/Li(2)S. The characterization of the three-membered redox series allows an analysis of redox trends, as well as a study of the effects of the amide donor environment on the [Fe(4)S(4)] core. Bis(trimethylsilyl)amide terminal ligation significantly stabilizes oxidized cluster redox states, permitting isolation of the uncommon [Fe(4)S(4)](3+) and unprecedented [Fe(4)S(4)](4+) weak-field cores. |
| Databáze: | OpenAIRE |
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