000169209 001__ 169209
000169209 005__ 20260223164759.0
000169209 0247_ $$2doi$$a10.1016/j.jcat.2026.116721
000169209 0248_ $$2sideral$$a148286
000169209 037__ $$aART-2026-148286
000169209 041__ $$aeng
000169209 100__ $$aPoves-Ruiz, Isabel
000169209 245__ $$aMechanistic Insights on the β-(Z) alkyne hydrosilylation by a NHC-based Cp*Rh(III) catalyst: from catalyst design to an alternative model for H-Si activation
000169209 260__ $$c2026
000169209 5060_ $$aAccess copy available to the general public$$fUnrestricted
000169209 5203_ $$aIn-depth studies on the residual hydrosilylation catalytic activity of samples of compound [Cp*RhI {(MeIm)2CH2}]+, bearing an unfunctionalized bis-NHC ligand, lead to the discovery of the excellent catalytic performance of the simple complex [Cp*RhI2(IMe)] (IMe = 1,3-dimethylimidozol-2-ylidene). This compound efficiently catalyzes the hydrosilylation of wide a range of terminal alkynes, with complete regio- and stereoselectivity toward the thermodynamically less stable β-(Z)-vinylsilane isomer. The reaction mechanism has been explored by DFT calculations. The reaction seems to proceed through an ionic outer-sphere mechanism, involving heterolytic activation of the hydrosilane assisted by the rhodium center and a solvent molecule (acetone). In the absence of acetone, a metal–ligand cooperation reaction pathway is proposed, in which the Cp* ligand acts as a proton-relay within the coordination sphere of the Rh(III) center. The cooperative activation of the hydrosilane by the metallocene moiety of the catalyst precursor generates a reactive Rh(I)–silyl intermediate bearing a pentamethylcyclopenta-1,3-diene ligand, [η4 -Cp*H], formed through protonation of the Cp* moiety.
000169209 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E42-23R$$9info:eu-repo/grantAgreement/ES/MCIU/PID2024-159030NA-I00$$9info:eu-repo/grantAgreement/ES/MICINN/PID2022-137208NB-I00
000169209 540__ $$9info:eu-repo/semantics/openAccess$$aby-nc$$uhttps://creativecommons.org/licenses/by-nc/4.0/deed.es
000169209 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000169209 700__ $$0(orcid)0000-0001-6675-7450$$aSánchez-Page, Beatriz
000169209 700__ $$0(orcid)0000-0002-0545-9107$$aJiménez, M. Victoria
000169209 700__ $$aGallegos, Miguel
000169209 700__ $$0(orcid)0000-0001-6089-6126$$aMunarriz, Julen$$uUniversidad de Zaragoza
000169209 700__ $$0(orcid)0000-0002-1735-6439$$aPassarelli, Vincenzo
000169209 700__ $$0(orcid)0000-0002-3327-0918$$aPérez-Torrente, Jesús J.$$uUniversidad de Zaragoza
000169209 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000169209 7102_ $$12012$$2755$$aUniversidad de Zaragoza$$bDpto. Química Física$$cÁrea Química Física
000169209 773__ $$g456 (2026), 116721 [13 pp.]$$pJ. catal.$$tJournal of Catalysis$$x0021-9517
000169209 8564_ $$s2432788$$uhttps://zaguan.unizar.es/record/169209/files/texto_completo.pdf$$yVersión publicada
000169209 8564_ $$s2619212$$uhttps://zaguan.unizar.es/record/169209/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000169209 909CO $$ooai:zaguan.unizar.es:169209$$particulos$$pdriver
000169209 951__ $$a2026-02-23-14:54:33
000169209 980__ $$aARTICLE