108284 20211115135503.0 doi 10.1021/jacs.0c07578 sideral 121169 ART-2020-121169 eng Esteruelas, M.A. (orcid)0000-0002-4829-7590 Kinetic Analysis and Sequencing of Si-H and C-H Bond Activation Reactions: Direct Silylation of Arenes Catalyzed by an Iridium-Polyhydride 2020 The 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. Access copy available to the general public Unrestricted info:eu-repo/grantAgreement/ES/DGA/E06-20R info:eu-repo/grantAgreement/ES/DGA/LMP148-18 info:eu-repo/grantAgreement/ES/MINECO-AEI-FEDER/CTQ2017-82935-P info:eu-repo/grantAgreement/ES/MINECO-AEI-FEDER/RED2018-102387-T info:eu-repo/semantics/openAccess All rights reserved http://www.europeana.eu/rights/rr-f/ 15.419 2020 CHEMISTRY, MULTIDISCIPLINARY 15 / 178 = 0.084 2020 Q1 T1 7.115 2020 Biochemistry 2020 Q1 Colloid and Surface Chemistry 2020 Q1 Chemistry (miscellaneous) 2020 Q1 Catalysis 2020 Q1 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion Martínez, A. (orcid)0000-0002-7292-8591 Oliván, M. (orcid)0000-0003-0381-0917 Oñate, E. (orcid)0000-0003-2094-719X 142, 45 (2020), 19119-19131 J. Am. Chem. Soc. Journal of the American Chemical Society 0002-7863 865272 http://zaguan.unizar.es/record/108284/files/texto_completo.pdf Postprint 2643474 http://zaguan.unizar.es/record/108284/files/texto_completo.jpg?subformat=icon icon Postprint oai:zaguan.unizar.es:108284 articulos driver 2021-11-15-08:52:43 ARTICLE