Reactions of bismuth-iron complex [Et4N]3[Bi{Fe(CO)4}4] with alkyl halides or dihalides: a general method for the synthesis of anionic complexes of the type [Et4N]2[RBi{Fe(CO)4}3] and the cyclic complexes R2Bi2Fe2(CO)8

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

“…Examples exist in which the starting materials are bismuth oxides, as exemplified by the highly charged cluster anion [{(CO) 4 (26) or the cyclic compound [R 2 Bi 2 Fe 2 (CO) 8 ] (27) (R = Me, Et, iPr, nBu, iBu, PhCH 2 , CH 2 Cl) ( Fig. 9) [86,87]. The cyclic species are favoured upon reaction with highly reactive electrophiles, however, as this reactivity is decreased, the former is increasingly favoured.…”

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

“…Further crystallization gave a small fraction of crystalline Fe 3 (CO) 12 [23]. [24,25] it was shown that after dissolution of crystals composed of trans-isomers a second series of signals occurred in the 1 H NMR spectrum suggesting cisetrans isomerisation in solution. However, for compound 1 exclusively broadening of the 1 H NMR signals at low temperature instead of a second series of signals was observed.…”

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

“…In the preparation of the ring complex [{ n BuBiFe(CO) 4 } 2 ] ( 2 ) from the reaction of [Et 4 N] 3 [Bi{Fe(CO) 4 } 4 ] with n BuBr in MeCN followed by acidification,7 we found that ultrasonication of 2 led to the formation of the polymeric product [ n BuBiFe(CO) 4 ] ∞ ( 1 ). An X‐ray structure analysis of crystals of 1 revealed an unusual mixed‐metal chain polymer which is composed of the n BuBiFe(CO) 4 groups with a novel ⋅⋅⋅‐Bi‐Fe‐⋅⋅⋅ chain (Figure 1).…”

“…Whereas the ring complex 2 is considered as the dimeric product of the monomer [ n BuBiFe(CO) 4 ] derived from the ionic complex [ n BuBi{Fe(CO) 4 } 3 ] 2− ,7 the polymer 1 can be viewed as the polymeric product that results from the cleavage (probably by radical processes) of BiFe bonds in 2 upon ultrasonication. The formation of 1 from 2 is reversible.…”

“…The coordination geometry at the bismuth center in 1 can be described as a pyramidal structure with an uncoordinated lone pair of electrons, which is seen in many other bismuth‐containing complexes such as [R 2 Bi 2 Fe 2 (CO) 8 ],7 [Et 4 N][BiFe 3 (CO) 10 ],10 and [Et 4 N] 2 [Bi 2 Fe 4 (CO) 13 ] 11. However, it is noteworthy that the Fe‐Bi‐Fe angle (156.46 (15)°) is unusually large and the sum of the angles at the bismuth center is about 350°, not far off being planar.…”