Palladium and ruthenium nanoparticles have been prepared following the organometallic precursor decomposition methodology, under dihydrogen pressure and in the presence of borane protected P-stereogenic phosphines. NMR (Nuclear Magnetic Resonance) monitoring of the corresponding syntheses has permitted to determine the optimal metal/ligand ratio for leading to small and well-dispersed nanoparticles. Exchange ligand reactions of the as-prepared materials have proven the strong interaction of the phosphines with the metal surface; only oxidative treatment using hydrogen peroxide could release the phosphine-based stabiliser from the metal surface. Pd and Ru nanoparticles have been evaluated in hydrogenation reactions, confirming the robustness of the stabilisers, which selectively permitted the hydrogenation of exocyclic C=C bonds, preventing the coordination of the aromatic rings and as a result, their hydrogenation.