Ana Maria Preda

Iron–Bismuth Halido Compounds: Molecules, Clusters, and Polymers

The pentamethylcyclopentadienyl substituted iron-bismuth halides [Bi{FeCp*(CO)2}X2] [X = Cl (1), Br (2), I (3); Cp* = η(5)-C5Me5] were synthesized starting from [FeCp*(CO)2]2 and BiX3 (X = Cl, Br), followed by halogen exchange reaction with KI in case of 3. From a reaction mixture of [FeCp*(CO)2]2 with BiCl3 in CH2Cl2 to which CH3CN had been added, a novel coordination polymer of the formula [FeCp*(CO)2(CH3CN)]2n[Bi4Cl14]n (4) was isolated. The change of the molar ratio from 1:1 to 1:2 in the reaction of [FeCp*(CO)2]2 with BiBr3 afforded the novel ionic complex [{FeCp*(CO)2Br]2[Bi6Br22{FeCp*(CO)2}]·CH2Cl2 (5·CH2Cl2). It is demonstrated that treatment of [FeCp*(CO)2X] (X = Cl, Br) with BiCl3 and BiBr3, respectively, is a more convenient route to synthesize the new halido bismuthates 4 and 5.

Hypervalent diorganoantimony(III) fluorides via diorganoantimony(III) cations – a general method of synthesis

Novel diorganoantimony(III) fluorides containing ligands with pendant arms, R2SbF (5), (R)PhSbF (6) [R = 2-(2′,6′-iPr2C6H3NCH)C6H4], R′′2SbF (7) and (R′′)PhSbF (8) [R′′ = 2-(Me2NCH2)C6H4], were prepared via the ionic derivatives [R2Sb]+[PF6]− (1), [(R)PhSb]+[PF6]− (2), [R′′2Sb]+[SbF6]− (4) and [(R′′)PhSb]+[SbF6]− (obtained in situ) by treatment with [Bu4N]F·3H2O. The ionic species used as starting materials as well as [R′2Sb]+[PF6]− (3) [R′ = 2-(2′,4′,6′-Me3C6H2NCH)C6H4] were obtained from the corresponding bromides or chlorides and Tl[PF6] or Ag[SbF6]. The compounds were investigated by multinuclear NMR spectroscopy in solution, MS and IR spectroscopy in the solid state. The molecular structures of the ionic species 1·2CH2Cl2 and 3·2CHCl3 as well as of the fluorides 5–8 were determined by single-crystal X-ray diffraction.

Two in one: the bismuth bromido clusters in [Bi6Cp*6Br9][Bi7Br24]

Abstract The reaction of [FeCp*(CO)2]2 in CH2Cl2 with BiBr3 in a 1:1 molar ratio gave the novel bismuth compound [Bi6Cp*6Br9][Bi7Br24] (1), which is composed of a cationic and an anionic bismuth bromido cluster: the cation is based on a hexanuclear bismuth {Bi6}-octahedron and the anion showing the first heptanuclear bismuth-bromido cluster within the class of bromido bismuthates.