000108332 001__ 108332
000108332 005__ 20230914083305.0
000108332 0247_ $$2doi$$a10.1021/acscatal.0c03295
000108332 0248_ $$2sideral$$a122230
000108332 037__ $$aART-2020-122230
000108332 041__ $$aeng
000108332 100__ $$0(orcid)0000-0001-6675-7450$$aSánchez-Page, B.
000108332 245__ $$aß-(Z) Selectivity Control by Cyclometalated Rhodium(III)-Triazolylidene Homogeneous and Heterogeneous Terminal Alkyne Hydrosilylation Catalysts
000108332 260__ $$c2020
000108332 5060_ $$aAccess copy available to the general public$$fUnrestricted
000108332 5203_ $$aThe cyclometalated Rh(III)-NHC compounds [Cp*RhI(C, C')-Triaz] (Triaz = 1, 4-diphenyl-3-methyl-1, 2, 3-triazol-5-ylidene) and [Cp*RhI(C, C')-Im] (Im = 1-phenyl-3-methyl-imidazol-2-ylidene) are efficient catalysts for the hydrosilylation of terminal alkynes with complete regio- and stereoselectivity toward the thermodynamically less stable ß-(Z)-vinylsilane isomer at room temperature in chloroform or acetone. Catalyst [Cp*RhI(C, C')-Triaz] shows a superior catalytic performance in terms of activity and has been applied to the hydrosilylation of a range of linear 1-alkynes and phenylacetylene derivatives with diverse hydrosilanes, including HSiMePh2, HSiMe2Ph, HSiEt3, and the bulkier heptamethylhydrotrisiloxane (HMTS), to afford the corresponding ß-(Z)-vinylsilanes in quantitative yields. The graphene-based hybrid material TRGO-Triaz-Rh(III), featuring cyclometalated [Cp*RhI(C, C')-Triaz] (Triaz = 1, 4-diphenyl-3-methyl-1, 2, 3-triazol-5-ylidene) rhodium(III) complexes covalently immobilized through the triazolylidene linker, has been prepared by metalation of the trimethylsilyl-protected 3-methyl-4-phenyl-1, 2, 3-triazolium iodide functionalized graphene oxide material, TRGO-Triaz, with [Cp*RhCl2]2 using sodium tert-butoxide as base. The coordination sphere of the supported rhodium(III) complexes has been determined by means of XPS and extended X-ray absorption fine structure (EXAFS) spectroscopy, showing the replacement of the iodido ligand by O-functionalities on the carbon wall. In sharp contrast with the homogeneous catalyst, the heterogeneous hybrid catalyst TRGO-Triaz-Rh(III) is not active at room temperature although it shows an excellent catalytic performance at 60 °C. In addition, the hybrid catalyst TRGO-Triaz-Rh(III) has shown an excellent recyclability, allowing at least six catalytic runs in the hydrosilylation of oct-1-yne with HSiMePh2 in acetone with complete selectivity to the ß-(Z)-vinylsilane product. The reaction mechanism for the molecular catalyst [Cp*RhI(C, C')-Triaz] has been explored by means of DFT calculations, pointing to a metal-ligand bifunctional mechanism involving reversible cyclometalation that is competitive with a noncooperative pathway. The proposed mechanism entails the Rh-CAr assisted hydrosilane activation to afford a reactive Rh-silyl intermediate that leads to a (E)-silylvinylene intermediate after alkyne insertion and a metallacyclopropene-driven isomerization. The release of the ß-(Z)-vinylsilane product can occur by a reversible cyclometalation mechanism involving s-CAM with the CAr-H bond or, alternatively, the Si-H bond of an external hydrosilane. The energy barrier for the latter is 1.2 kcal·mol-1 lower than that of the CAr-H bond, which results in a small energy span difference that makes both pathways competitive under catalytic conditions.
000108332 536__ $$9info:eu-repo/grantAgreement/ES/MICINN-FEDER/RTI2018-098537-B-C22$$9info:eu-repo/grantAgreement/ES/MICINN-FEDER/PID2019-103965GB-I00$$9info:eu-repo/grantAgreement/ES/MICINN-FEDER/CTQ2016-75884-P$$9info:eu-repo/grantAgreement/ES/DGA-FSE/E42-20R$$9info:eu-repo/grantAgreement/ES/DGA-FSE/E12-20R
000108332 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttp://creativecommons.org/licenses/by/3.0/es/
000108332 590__ $$a13.084$$b2020
000108332 591__ $$aCHEMISTRY, PHYSICAL$$b15 / 162 = 0.093$$c2020$$dQ1$$eT1
000108332 592__ $$a4.897$$b2020
000108332 593__ $$aChemistry (miscellaneous)$$c2020$$dQ1
000108332 593__ $$aCatalysis$$c2020$$dQ1
000108332 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000108332 700__ $$0(orcid)0000-0001-6089-6126$$aMunarriz, J.
000108332 700__ $$0(orcid)0000-0002-0545-9107$$aJiménez, M.V.$$uUniversidad de Zaragoza
000108332 700__ $$0(orcid)0000-0002-3327-0918$$aPérez-Torrente, J.J.$$uUniversidad de Zaragoza
000108332 700__ $$0(orcid)0000-0002-9706-3272$$aBlasco, J.$$uUniversidad de Zaragoza
000108332 700__ $$aSubias, G.
000108332 700__ $$0(orcid)0000-0002-1735-6439$$aPassarelli, V.$$uUniversidad de Zaragoza
000108332 700__ $$aÁlvarez, P.
000108332 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000108332 7102_ $$12003$$2395$$aUniversidad de Zaragoza$$bDpto. Física Materia Condensa.$$cÁrea Física Materia Condensada
000108332 773__ $$g10, 22 (2020), 13334-13351$$pACS catal.$$tACS CATALYSIS$$x2155-5435
000108332 8564_ $$s2473306$$uhttps://zaguan.unizar.es/record/108332/files/texto_completo.pdf$$yPostprint
000108332 8564_ $$s1275924$$uhttps://zaguan.unizar.es/record/108332/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000108332 909CO $$ooai:zaguan.unizar.es:108332$$particulos$$pdriver
000108332 951__ $$a2023-09-13-10:55:48
000108332 980__ $$aARTICLE