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).