Synthesis, characterization, and reactivity of iron carbonyl clusters containing bismuth or antimony. Crystal structures of isomorphous [Et4N][BiFe3Cr(CO)17] and [Et4N][SbFe3Cr(CO)17] and the ring complex Bi2Fe2(CO)8Me2

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

“…Crystals of 1 are sensitive to air and moisture and decompose slowly in solution to give Fe 3 (CO) 12 [23] and Bi 2 Fe 3 (CO) 9 [12] as was confirmed by single crystal X-ray diffraction analysis. Similarly, it was observed previously that [(CO) 4 FeBiCH 2 CMe 3 ] 2 [21] and [(CO) 4 FeBiMe] 2 [24] decompose to give Bi 2 Fe 3 (CO) 9 . The compound [(CO) 4 FeBi(OSiMe 2 t Bu)] 2 (1) crystallizes in the space group PÀ1…”

“…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.…”

“…Therefore, only compound 1a is discussed here. The molecular structure of 1a is composed of a [21,24,26]. In the Fe 2 Bi 2 parallelogram the BieBi distance amounts to 3.6400 (12) Å and is considered non-bonding.…”

Contents

“…There is a center of symmetry in the middle of an Sb 2 S 2 ring and a two-fold rotation axis parallel to, and passing through the antimony atoms of this four-membered ring. 2 , where R = Me [116], Ph [117] or Bu' [23]. The core framework of the clusters consists of Fe 2 Bi 2 parallellograms situated around a crystallographic center of symmetry.…”

Low‐Valent Organobismuth Compounds with Intramolecular Coordination: cyclo‐R3Bi3, cyclo‐R4Bi4, RBi[W(CO)5]2, and R4Bi2 [R = 2‐(Me2NCH2)C6H4]

“…[(RBiϭBiR){W(CO) 5 } 2 ]. [8] Monomeric bismuthinidenes have not been isolated, but RBi groups have been incorporated into cyclo-[RBiFe (CO) 4 ] 2 (R ϭ Me, [9] Ph, [10] iBu [11] ). The oxidation state of bismuth in these complexes is, however, ambiguous.…”