000108284 001__ 108284
000108284 005__ 20211115135503.0
000108284 0247_ $$2doi$$a10.1021/jacs.0c07578
000108284 0248_ $$2sideral$$a121169
000108284 037__ $$aART-2020-121169
000108284 041__ $$aeng
000108284 100__ $$0(orcid)0000-0002-4829-7590$$aEsteruelas, M.A.
000108284 245__ $$aKinetic Analysis and Sequencing of Si-H and C-H Bond Activation Reactions: Direct Silylation of Arenes Catalyzed by an Iridium-Polyhydride
000108284 260__ $$c2020
000108284 5060_ $$aAccess copy available to the general public$$fUnrestricted
000108284 5203_ $$aThe saturated trihydride IrH3{¿3-P, O, P-[xant(PiPr2)2]} (1; xant(PiPr2)2 = 9, 9-dimethyl-4, 5-bis(diisopropylphosphino)xanthene) coordinates the Si-H bond of triethylsilane, 1, 1, 1, 3, 5, 5, 5-heptamethyltrisiloxane, and triphenylsilane to give the s-complexes IrH3(¿2-H-SiR3){¿2-cis-P, P-[xant(PiPr2)2]}, which evolve to the dihydride-silyl derivatives IrH2(SiR3){¿3-P, O, P-[xant(PiPr2)2]} (SiR3 = SiEt3 (2), SiMe(OSiMe3)2 (3), SiPh3 (4)) by means of the oxidative addition of the coordinated bond and the subsequent reductive elimination of H2. Complexes 2-4 activate a C-H bond of symmetrically and asymmetrically substituted arenes to form silylated arenes and to regenerate 1. This sequence of reactions defines a cycle for the catalytic direct C-H silylation of arenes. Stoichiometric isotopic experiments and the kinetic analysis of the transformations demonstrate that the C-H bond rupture is the rate-determining step of the catalysis. As a consequence, the selectivity of the silylation of substituted arenes is generally governed by ligand-substrate steric interactions.
000108284 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E06-20R$$9info:eu-repo/grantAgreement/ES/DGA/LMP148-18$$9info:eu-repo/grantAgreement/ES/MINECO-AEI-FEDER/CTQ2017-82935-P$$9info:eu-repo/grantAgreement/ES/MINECO-AEI-FEDER/RED2018-102387-T
000108284 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000108284 590__ $$a15.419$$b2020
000108284 591__ $$aCHEMISTRY, MULTIDISCIPLINARY$$b15 / 178 = 0.084$$c2020$$dQ1$$eT1
000108284 592__ $$a7.115$$b2020
000108284 593__ $$aBiochemistry$$c2020$$dQ1
000108284 593__ $$aColloid and Surface Chemistry$$c2020$$dQ1
000108284 593__ $$aChemistry (miscellaneous)$$c2020$$dQ1
000108284 593__ $$aCatalysis$$c2020$$dQ1
000108284 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000108284 700__ $$0(orcid)0000-0002-7292-8591$$aMartínez, A.
000108284 700__ $$0(orcid)0000-0003-0381-0917$$aOliván, M.
000108284 700__ $$0(orcid)0000-0003-2094-719X$$aOñate, E.
000108284 773__ $$g142, 45 (2020), 19119-19131$$pJ. Am. Chem. Soc.$$tJournal of the American Chemical Society$$x0002-7863
000108284 8564_ $$s865272$$uhttps://zaguan.unizar.es/record/108284/files/texto_completo.pdf$$yPostprint
000108284 8564_ $$s2643474$$uhttps://zaguan.unizar.es/record/108284/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000108284 909CO $$ooai:zaguan.unizar.es:108284$$particulos$$pdriver
000108284 951__ $$a2021-11-15-08:52:43
000108284 980__ $$aARTICLE