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

Abstract

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).

Single‐Source Precursors for the Chemical Vapor Deposition of Iron Germanides

“…Synthesis of di-μ-dichlorogermylene-bis(tetracarbonyliron) 2: GeCl 2 / 1,4-dioxane complex (1.1 g, 4.6 mmol) and Fe 2 (CO) 9 (1.7 g, 4.6 mmol) were cooled to À 78 °C and cold 100 mL thf were added. The greenish brown suspension was allowed to warm within 3 h and stirring continued overnight.…”

“…obtained Fe 5 Ge 3 nanoparticles by thermal decomposition of germylene/ironcarbonyl complexes in mesitylene [8] . [BMIm][(GeI 3 ) 2 Fe(CO) 3 I] (BMIm=1‐butyl‐3‐methylimidazolium) has served as an single source precursor (SSP) for bimetallic Ge−Fe nanoparticles in ionic liquids [9] . A chemical vapor transport reaction of elemental Ge and FeI 2 resulted in nanowires of ferromagnetic Fe 4 Ge 3 or FeGe depending on the experimental conditions [10]…”

“…[8] [BMIm][(GeI 3 ) 2 Fe(CO) 3 I] (BMIm = 1-butyl-3-methylimidazolium) has served as an single source precursor (SSP) for bimetallic GeÀ Fe nanoparticles in ionic liquids. [9] A chemical vapor transport reaction of elemental Ge and FeI 2 resulted in nanowires of ferromagnetic Fe 4 Ge 3 or FeGe depending on the experimental conditions. [10] In contrast to the corresponding processes for the preparation of transition metal silicides such as FeSi, CoSi and MnSi, [11] the single source chemical vapor deposition (CVD) of transition metal germanides is completely unexplored despite numerous iron-and germanium-containing molecular species (Scheme 1), [12] which are not only sufficiently small and should hence provide a suitable evaporation rate but also contain ligands that should easily cleave at elevated temperatures.…”

A Comprehensive Study on Molecular Interactions of l-Ascorbic Acid/Nicotinic Acid in Aqueous [BMIm]Br at Varying Temperatures and Compositions: Spectroscopic and Thermodynamic Insights

“…They possess exclusive characteristics such as ultralow vapor pressure, extensive liquid range, thermal stability, non-flammability, a melting point below 373.15 K, enormous solvation ability, dormant application in electrochemical fields, and a variety of physicochemical properties. For these reasons, ILs are green alternatives to conventional toxic organic solvents and so are appropriated in organic synthesis and catalysis, − in chromatography for extraction and separation, − gas capture, − nanoscience, and in electrochemistry. − As a consequence of these fascinating properties, it has been feasible to develop the nontoxic, task-specific fluid for industrial prospects. A variation in the nature of cation/anion/moieties attributed to each ion leads to changes in the physical and chemical properties of ILs .…”