132177 20260217205454.0 doi 10.1021/acs.organomet.3c00498 sideral 137461 ART-2024-137461 eng Gómez-España, Alejandra Rhodium Complexes with a Pyridine-2-yloxy-silyl-Based N,Si-Ligand: Bonding Situation and Activity as Alkene Hydrogenation Catalysts 2024 Access copy available to the general public Unrestricted Rh(III) complexes [Rh(H)(X)(κ2-NSitBu2OPy)(L)] (X = Cl, L = PCy3, 2a; PHtBu2, 2b; X = OTf, L = PCy3, 3a; PHtBu2, 3b) (NSitBu2OPy = 4-methylpyridin-2-yloxy-ditertbutylsilyl) have been prepared and characterized by means of elemental analysis and nuclear magnetic resonance (NMR) spectroscopy. The solid-state structures of complexes 2a, 2b, and 3a have been determined by X-ray diffraction studies. Computational analyses of the bonding situation of these species evidence the electron-sharing nature of the Rh–Si bond and the significant role of the electrostatic component in the interaction between the transition metal fragment [Rh(H)(PR3)(X)]• and the [NSitBu2OPy]• ligand. In addition, a comparative study of the activity of 2a, 2b, 3a, 3b, and related iridium species as catalysts for the hydrogenation of olefins has been performed. The best catalytic results have been obtained when using the Rh(III) species 3a, with triflate and PCy3 ligands, as catalyst. Computational density functional theory studies show that the formation of the alkane is thermodynamically favored and that the rate-limiting step corresponds to the hydrogen activation, which takes place via a σ-complex-assisted metathesis mechanism. info:eu-repo/semantics/openAccess by https://creativecommons.org/licenses/by/4.0/deed.es 2.9 2024 CHEMISTRY, ORGANIC 14 / 57 = 0.246 2024 Q1 T1 CHEMISTRY, INORGANIC & NUCLEAR 17 / 43 = 0.395 2024 Q2 T2 0.676 2024 Inorganic Chemistry 2024 Q2 Physical and Theoretical Chemistry 2024 Q2 Organic Chemistry 2024 Q2 5.1 2024 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion García-Orduña, Pilar (orcid)0000-0002-7063-1292 Lahoz, Fernando J. (orcid)0000-0001-8054-2237 Fernández, Israel Fernández-Álvarez, Francisco J. Universidad de Zaragoza (orcid)0000-0002-0497-1969 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 43, 3 (2024), 402-413 Organometallics Organometallics 0276-7333 3524931 http://zaguan.unizar.es/record/132177/files/texto_completo.pdf Versión publicada 3110631 http://zaguan.unizar.es/record/132177/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:132177 articulos driver 2026-02-17-20:19:56 ARTICLE