Ge−Fe Carbonyl Cluster Compounds: Ionic Liquids‐Based Synthesis, Structures, and Properties

Nine Ge−Fe carbonyl cluster compounds are prepared via ionic liquids‐based synthesis. This includes the novel compounds [EMIm][Fe(CO)$_{3}$I(GeI$_{3}$)], [EHIm][Fe(CO)$_{3}$I(GeI$_{3}$)], [BMIm][GeI$_{2}${Fe(CO)$_{4}$}$_{2}$(μ‐I)][AlCl$_{4}$]$_{2}$, [GeI$_{2}${Fe(CO)$_{4}$}$_{2}$(μ‐I)][Fe(AlBr$_{4}$)$_{3}$], [BMIm]$_{2}$[(FeI$_{2}$)$_{0.75}${Fe(CO)$_{2}$I(GeI$_{3}$)$_{2}$}$_{2}$], and [EHIm][Fe(CO)$_{4}$(GeI$_{2}$)$_{2}$Fe(CO)$_{3}$GeI$_{3}$] as well as the previously reported compounds (Fe(CO)$_{4}$(GeI$_{3}$)$_{2}$, FeI$_{4}${GeI$_{3}$Fe(CO)$_{3}$}$_{2}$, and Ge$_{12}${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][{GeI$_{3}$}$_{2}$Fe(CO)$_{3}$I], 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).