000132177 001__ 132177
000132177 005__ 20240301161206.0
000132177 0247_ $$2doi$$a10.1021/acs.organomet.3c00498
000132177 0248_ $$2sideral$$a137461
000132177 037__ $$aART-2024-137461
000132177 041__ $$aeng
000132177 100__ $$aGómez-España, Alejandra
000132177 245__ $$aRhodium Complexes with a Pyridine-2-yloxy-silyl-Based N,Si-Ligand: Bonding Situation and Activity as Alkene Hydrogenation Catalysts
000132177 260__ $$c2024
000132177 5060_ $$aAccess copy available to the general public$$fUnrestricted
000132177 5203_ $$aRh(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.
000132177 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttp://creativecommons.org/licenses/by/3.0/es/
000132177 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000132177 700__ $$0(orcid)0000-0002-7063-1292$$aGarcía-Orduña, Pilar
000132177 700__ $$0(orcid)0000-0001-8054-2237$$aLahoz, Fernando J.
000132177 700__ $$aFernández, Israel
000132177 700__ $$0(orcid)0000-0002-0497-1969$$aFernández-Álvarez, Francisco J.$$uUniversidad de Zaragoza
000132177 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000132177 773__ $$g43, 3 (2024), 402-413$$pOrganometallics$$tOrganometallics$$x0276-7333
000132177 8564_ $$s3524931$$uhttps://zaguan.unizar.es/record/132177/files/texto_completo.pdf$$yVersión publicada
000132177 8564_ $$s3110631$$uhttps://zaguan.unizar.es/record/132177/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000132177 909CO $$ooai:zaguan.unizar.es:132177$$particulos$$pdriver
000132177 951__ $$a2024-03-01-14:51:17
000132177 980__ $$aARTICLE