Cubane-like Bismuth-iron cluster: synthesis, X-ray crystal structure and theoretical characterization of the [Bi4Fe8(CO)28]4- Anion
The reaction of cyclo-Bi4[Si(SiMe3)3]4 (1) with Na2[Fe(CO)4] in the presence of nBu4NCl leads to the formation of the cage compound [nBu4N]4[Bi4Fe8(CO)28] (2). According to X-ray single-crystal structure analysis, the faces of the tetrahedral Bi4 core are capped by Fe(CO)3 moieties in a μ3 fashion t...
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| Hauptverfasser: | , , |
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| Dokumenttyp: | Article (Journal) |
| Sprache: | Englisch |
| Veröffentlicht: |
06 July 2010
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| In: |
European journal of inorganic chemistry
Year: 2010, Heft: 20, Pages: 3212-3219 |
| ISSN: | 1099-0682 |
| DOI: | 10.1002/ejic.201000215 |
| Online-Zugang: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1002/ejic.201000215 Verlag, lizenzpflichtig, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/ejic.201000215 
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| Verfasserangaben: | Kirill Yu. Monakhov, Thomas Zessin, and Gerald Linti |
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| 246 | 3 | 3 | |a Cubane-like Bismuth-iron cluster$dsynthesis, X-ray crystal structure and theoretical characterization of the [Bi 4 Fe 8 (CO) 28] 4- Anion |
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| 520 | |a The reaction of cyclo-Bi4[Si(SiMe3)3]4 (1) with Na2[Fe(CO)4] in the presence of nBu4NCl leads to the formation of the cage compound [nBu4N]4[Bi4Fe8(CO)28] (2). According to X-ray single-crystal structure analysis, the faces of the tetrahedral Bi4 core are capped by Fe(CO)3 moieties in a μ3 fashion to give a cubanoid Bi4Fe4 framework. The four Fe(CO)4 fragments are μ1-coordinated to bismuth, each. With 12 skeletal electron pairs the [Bi4Fe8(CO)28]4- anion (2a) is a Bi4Fe4 cubane. The negative charge is localized within cluster 2a according to the NBO analysis of its derivatives. The strength of metal-ligand interactions Bi-μ3-Fe(CO)3 is responsible for the size of the cluster's cubic core. NICS computations at the cage centers of considered molecules show that 2a has paratropic character, whereas removal of four μ1-Fe(CO)4 fragments from latter causes spherical aromaticity of the modified clusters [Bi4Fe4(CO)12]4- (2aa) and [Bi4Fe4(CO)12]2+ (2ab), mediated by a Bi4 cluster π orbital. | ||
| 650 | 4 | |a Aromaticity | |
| 650 | 4 | |a Bismuth | |
| 650 | 4 | |a Cluster compounds | |
| 650 | 4 | |a Density functional calculations | |
| 650 | 4 | |a Iron | |
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