Metal(II) Formates (M = Fe,Co, Ni,and Cu) Stabilized by Tetramethylethylenediamine (tmeda): Convenient Molecular Precursors for the Synthesis of Supported Nanoparticles

γ‐Alumina supported 3d transition‐metal nanoparticles are commonly used catalysts for several industrial reactions, such as Fischer‐Tropsch, reforming, methanation, and hydrogenation reactions. However, the activity of such catalyst is often limited by the low metal dispersion and a high content of irreducible metal, inherent to the conventional preparation methods in aqueous phase. In this context, we have recently shown that [{Ni(μ²‐OCHO)(OCHO)(tmeda)}₂(μ²‐OH₂)] (tmeda=tetramethylethylenediamine) is a suitable molecular precursor for the formation of 1–2 nm large nanoparticles onto alumina. Here, we explore the synthesis of the corresponding Fe, Co, and Cu molecular precursors, namely [{Fe(μ²‐OCHO)(OCHO)(tmeda)}₄], [{Co(μ²‐OCHO)(OCHO)(tmeda)}₂(μ²‐OH₂ )], [Cu(κ²‐OCHO)₂(tmeda)], which are, like the Ni precursor, soluble in a range of solvents, rendering them convenient metal precursors for the preparation of supported metallic nanoparticles on γ‐alumina. Using a specific adsorption of the molecular precursor on γ‐alumina in a suitable organic solvent, treatment under H₂ provides small and narrowly distributed Fe (2.5±0.9 nm), Co (3.0±1.2 nm), Ni (1.7±0.5 nm), and Cu (2.1±1.5 nm) nanoparticles. XAS shows that the proportion of MAl₂O₄ (M = Co, Ni, Cu) is small, thus illustrating the advantage of using these tailor‐made molecular precursors.