000127883 001__ 127883
000127883 005__ 20240209144725.0
000127883 0247_ $$2doi$$a10.1021/acscatal.0c01582
000127883 0248_ $$2sideral$$a119156
000127883 037__ $$aART-2020-119156
000127883 041__ $$aeng
000127883 100__ $$0(orcid)0000-0002-5465-4873$$aPuerta-Oteo, R.
000127883 245__ $$aCarboxylate-Assisted ß-(Z) Stereoselective Hydrosilylation of Terminal Alkynes Catalyzed by a Zwitterionic Bis-NHC Rhodium(III) Complex
000127883 260__ $$c2020
000127883 5060_ $$aAccess copy available to the general public$$fUnrestricted
000127883 5203_ $$aThe zwitterionic compound [Cp*RhCl{(MeIm)2CHCOO}] is an efficient catalyst for the hydrosilylation of terminal alkynes with excellent regio- and stereoselectivity toward the less thermodynamically stable ß-(Z)-vinylsilane isomer under mild reaction conditions. A broad range of linear 1-alkynes, cycloalkyl acetylenes, and aromatic alkynes undergo the hydrosilylation with HSiMe2Ph to afford the corresponding ß-(Z)-vinylsilanes in quantitative yields in short reaction times. The reaction of aliphatic alkynes with HSiEt3 is slower, resulting in a slight decrease of selectivity toward the ß-(Z)-vinylsilane product, which is still greater than 90%. However, a significant selectivity decrease is observed in the hydrosilylation of aromatic alkynes because of the ß-(Z) ¿ ß-(E) vinylsilane isomerization. Moreover, the hydrosilylation of bulky alkynes, such as t-Bu-CCH or Et3SiCCH, is unselective. Experimental evidence suggests that the carboxylate function plays a key role in the reaction mechanism, which has been validated by means of density functional theory calculations, as well as by mass spectrometry and labeling studies. On the basis of previous results, we propose an ionic outer-sphere mechanism pathway in which the carboxylate fragment acts as a silyl carrier. Namely, the hydrosilylation mechanism entails the heterolytic activation of the hydrosilane assisted by the carboxylate function to give the hydrido intermediate [Cp*RhH{(MeIm)2CHCOO-SiR3}]+. The transference of the silylium moiety from the carboxylate to the alkyne results in the formation of a flat ß-silyl carbocation intermediate that undergoes a hydride transfer from the Rh(III) center to generate the vinylsilane product. The outstanding ß-(Z) selectivity results from the minimization of the steric interaction between the silyl moiety and the ligand system in the hydride transfer transition state. Copyright
000127883 536__ $$9info:eu-repo/grantAgreement/ES/DGA-FSE/Building Europe from Aragon$$9info:eu-repo/grantAgreement/ES/DGA-FSE/E42-17R$$9info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2016-75884-P
000127883 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000127883 590__ $$a13.084$$b2020
000127883 591__ $$aCHEMISTRY, PHYSICAL$$b15 / 162 = 0.093$$c2020$$dQ1$$eT1
000127883 592__ $$a4.897$$b2020
000127883 593__ $$aChemistry (miscellaneous)$$c2020$$dQ1
000127883 593__ $$aCatalysis$$c2020$$dQ1
000127883 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000127883 700__ $$0(orcid)0000-0001-6089-6126$$aMunarriz, J.
000127883 700__ $$0(orcid)0000-0001-5823-7965$$aPolo, V.$$uUniversidad de Zaragoza
000127883 700__ $$0(orcid)0000-0002-0545-9107$$aJiménez, M.V.$$uUniversidad de Zaragoza
000127883 700__ $$0(orcid)0000-0002-3327-0918$$aPérez-Torrente, J.J.$$uUniversidad de Zaragoza
000127883 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000127883 7102_ $$12012$$2755$$aUniversidad de Zaragoza$$bDpto. Química Física$$cÁrea Química Física
000127883 773__ $$g10, 13 (2020), 7367-7380$$pACS catal.$$tACS CATALYSIS$$x2155-5435
000127883 8564_ $$s1006777$$uhttps://zaguan.unizar.es/record/127883/files/texto_completo.pdf$$yPostprint
000127883 8564_ $$s3039706$$uhttps://zaguan.unizar.es/record/127883/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000127883 909CO $$ooai:zaguan.unizar.es:127883$$particulos$$pdriver
000127883 951__ $$a2024-02-09-14:44:54
000127883 980__ $$aARTICLE