Metallic Ru, Rh, and Ir nanoparticles were prepared by the decomposition of organometallic precursors under H2 pressure in the presence of 1,3-diphosphite ligands, derived from carbohydrates, as stabilizing agents. Structural modifications to the diphosphite backbone were found to influence the nanoparticles′ size, dispersion, and catalytic activity. In the hydrogenation of o- and m-methylanisole, the Rh nanoparticles showed higher catalytic activity than the corresponding Ru nanoparticles. The Ir nanoparticles presented the lowest catalytic activity of the series. In all cases, the hydrogenation of o-methylanisole gave total selectivity for the cis-product, however, the ee of the product was always less than 6 %. A maximum of 81 % cis-selectivity was obtained for the hydrogenation of m-methylanisole, however, no asymmetric induction was observed. These results show that the catalytic activity is affected by a combination of influences from the substrate, the diphosphite ligands, and the metallic nanoparticles.