Search

The carbonyl cluster compound [GeRu6(CO)18HI] is unique in regard to its structure and bonding with a GeRu6 cluster core, a planar GeRu4HI unit, extensive multi‐center bonding, and an aromatic ring current similar to benzene (9‐10 nA T−1). The open‐shell cluster core is a Ge‐centered five‐membered Ru4(Ru2) ring with CO ligands and an additional H and I atom, each bridging two Ru atoms on opposite sides of the cluster core. The compound is prepared at 130 °C in a weakly‐coordinating ionic liquid. [ABSTRACT FROM AUTHOR]

Nine Ge−Fe carbonyl cluster compounds are prepared via ionic liquids‐based synthesis. This includes the novel compounds [EMIm][Fe(CO)3I(GeI3)], [EHIm][Fe(CO)3I(GeI3)], [BMIm][GeI2{Fe(CO)4}2(μ‐I)][AlCl4]2, [GeI2{Fe(CO)4}2(μ‐I)][Fe(AlBr4)3], [BMIm]2[(FeI2)0.75{Fe(CO)2I(GeI3)2}2], and [EHIm][Fe(CO)4(GeI2)2Fe(CO)3GeI3] as well as the previously reported compounds (Fe(CO)4(GeI3)2, FeI4{GeI3Fe(CO)3}2, and Ge12{Fe(CO)3}8(μ‐I)4 (EMIm: 1‐ethyl‐3‐methylimidazolium, EHIm: 1‐ethylimidazolium, BMIm: 1‐butyl‐3‐methylimidazolium). With this series of compounds, a comparison of synthesis conditions and structural features is possible and, for instance, allows correlating the composition and structure of the respective Ge−Fe carbonyl cluster compounds with the type and acidity of the ionic liquid. With [EMIm][{GeI3}2Fe(CO)3I], moreover, we can exemplarily show the thermal decomposition as a single‐source precursor in the ionic liquid, resulting in bimetallic Ge−Fe nanoparticles with small size and narrow size distribution (7.0±1.4 nm). [ABSTRACT FROM AUTHOR]

Dark red and brick red transparent crystals of FeI4{GeI3Fe(CO)3}2 ( 1) and (GeI3)2Fe(CO)4 ( 2) were obtained by reacting GeI4 and Fe2(CO)9 or Fe3(CO)12 in a mixture of [BMIM]Cl and AlCl3 as ionic liquid (BMIm = 1-butyl-3-methylimidazolium). According to X-ray structure analysis based on single crystals, the title compounds exhibit cluster units with Fe-Ge bonds. FeI4{GeI3Fe(CO)3}2 consists of two GeI2I1/2-Fe(CO)3I2/2 units that are interlinked by a distorted octahedral FeI6/2 group. (GeI3)2Fe(CO)4 consists of two GeI3 units that are connected by a square planar Fe(CO)4 group with a linear Ge-Fe-Ge unit. Depending on the synthesis conditions, interestingly, (GeI3)2Fe(CO)4 crystallizes either in P21/ n ( 2a) or in P 1 ( 2b). 2a exhibits a more dense packing, whereas 2b exhibits shorter intermolecular I-I distances. Both title compounds are temperature labile and highly sensitive to oxygen, moisture and illumination, including X-ray irradiation. They decompose with release of CO in absence of certain CO atmosphere. In addition to crystal structure analysis the compounds were characterized by energy dispersive X-ray (EDX) analysis, thermogravimetry (TG) and infrared spectroscopy (FT-IR). [ABSTRACT FROM AUTHOR]