A Unique Bismuth–Iron Chain Polymer Containing the ⋅⋅⋅‐Bi‐Fe‐⋅⋅⋅ Link: Formation and Structure of [ n BuBiFe(CO) ₄ ] _∞

Abstract

A unique zigzag ⋅⋅⋅‐Bi‐Fe‐⋅⋅⋅ chain forms the basis of the structure of [nBuBiFe(CO)4]∞ (1; see picture), which was characterzized by single‐crystal X‐ray diffraction. Compound 1 was isolated from the ultrasonication of the dimeric product [{nBuBiFe(CO)4}2] from the reaction of [Et4N]3[Bi{Fe(CO)4}4] with nBuBr followed by acidification with HOAc.

Discovery of FeBi2

“…For comparison, molecular Fe–Bi bonds are known to exist in iron carbonyl species, where they possess lengths up to 2.85 Å. 21−23 The sum of the covalent radii of iron and bismuth is 1.25 Å ( r Fe ) + 1.46 Å ( r Bi ) = 2.71 Å, 24 which compares very well with the value obtained for Fe–Bi in FeBi 2 at the formation pressure. We should note that covalent radii may underestimate bond lengths in intermetallic compounds, due to the increased electron delocalization across the structure coupled with the larger number of interactions common in intermetallic compounds, as compared with the highly directional interactions found in molecules.…”

Synthesis, structure and reactivity of complexes containing a transition metal–bismuth bond

“…Shieh et al succeeded in obtaining the first example of a continuous · · ·-Bi-Fe-· · · interaction, by way of the polymeric species [nBuBiFe(CO) 4 ] ∞ , generated by ultrasonification of [{nBuBiFe(CO) 4 } 2 ] [179]. This reaction is thought to proceed via radical cleavage of the Fe-Bi bond in the dimeric species.…”

Novel carbonyl iron–bismuth clusters – synthesis, structure, CO2 insertion and potential as molecular precursors for BiFeO3

“…Breunig and coworkers also reported several complexes that were obtained in the reaction of dibismuthanes or cyclobismuthanes with metal carbonyls [21]. For example, the reaction of tetra(neopentyl)dibismuthane with [Fe 2 (CO) 9 [22]. However, similar Fe-containing compounds with alkoxides or related ligands were not reported so far.…”