Cubane‐Like Bismuth‐Iron Cluster: Synthesis, X‐ray Crystal Structure and Theoretical Characterization of the [Bi 4 Fe 8 (CO) 28 ] 4– Anion

Autor: Gerald Linti, Kirill Yu. Monakhov, Thomas Zessin
Rok vydání: 2010
Předmět:
Zdroj: European Journal of Inorganic Chemistry. 2010:3212-3219
ISSN: 1099-0682
1434-1948
Popis: The reaction of cyclo-Bi 4 [Si(SiMe 3 ) 3 ] 4 (1) with Na 2 [Fe(CO) 4 ] in the presence of nBu 4 NCl leads to the formation of the cage compound [nBu 4 N] 4 [Bi 4 Fe 8 (CO) 28 ] (2). According to X-ray single-crystal structure analysis, the faces of the tetrahedral Bi 4 core are capped by Fe(CO) 3 moieties in a μ 3 fashion to give a cubanoid Bi 4 Fe 4 framework. The four Fe(CO) 4 fragments are μ 1 -coordinated to bismuth, each. With 12 skeletal electron pairs the [Bi 4 Fe 8 (CO) 28 ] 4- anion (2a) is a Bi 4 Fe 4 cubane. The negative charge is localized within cluster 2a according to the NBO analysis of its derivatives. The strength of metal-ligand interactions Bi-μ 3 -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 para-tropic character, whereas removal of four μ 1 -Fe(CO) 4 fragments from latter causes spherical aromaticity of the modified clusters [Bi 4 Fe 4 (CO) 12 ] 4- (2aa) and [Bi 4 Fe 4 (CO) 12 ] 2+ (2ab), mediated by a Bi 4 cluster π orbital.
Databáze: OpenAIRE
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