A Simple and Versatile Approach for the Low‐Temperature Synthesis of Transition Metal Phosphide Nanoparticles from Metal Chloride Complexes and P(SiMe₃)₃

Abstract Metal chloride complexes react with tris(trimethylsilyl)phosphine under mild condition to produce metal phosphide (TMP) nanoparticles (NPs), and chlorotrimethylsilane as a byproduct. The formation of Si–Cl bonds that are stronger than the starting M‐Cl bonds acts as a driving force for the reaction. The potential of this strategy is illustrated through the preparation of ruthenium phosphide NPs using [RuCl₂(cymene)] and tris(trimethylsilyl)phosphine at 35 °C. Characterization with a combination of techniques including electron microscopy (EM), X‐ray absorption spectroscopy (XAS), and solid‐state nuclear magnetic resonance (NMR) spectroscopy, evidences the formation of small (diameter of 1.3 nm) and amorphous NPs with an overall Ru₅₀P₅₀ composition. Interestingly, these NPs can be easily immobilized on functional support materials, which is of great interest for potential applications in catalysis and electrocatalysis. Mo₅₀P₅₀ and Co₅₀P₅₀ NPs can also be synthesized following the same strategy. This approach is simple and versatile and paves the way toward the preparation of a wide range of transition metal phosphide nanoparticles under mild reaction conditions.