62080 20230914083222.0 doi 10.1039/c6sc04899d sideral 101155 ART-2017-101155 eng Rubio-Pérez, L. (orcid)0000-0002-2176-0864 A well-defined NHC-Ir(III) catalyst for the silylation of aromatic C-H bonds: Substrate survey and mechanistic insights 2017 Access copy available to the general public Unrestricted A well-defined NHC-Ir(iii) catalyst, [Ir(H)2(IPr)(py)3][BF4] (IPr = 1, 3-bis-(2, 6-diisopropylphenyl)imidazol-2-ylidene), that provides access to a wide range of aryl- and heteroaryl-silanes by intermolecular dehydrogenative C-H bond silylation has been prepared and fully characterized. The directed and non-directed functionalisation of C-H bonds has been accomplished successfully using an arene as the limiting reagent and a variety of hydrosilanes in excess, including Et3SiH, Ph2MeSiH, PhMe2SiH, Ph3SiH and (EtO)3SiH. Examples that show unexpected selectivity patterns that stem from the presence of aromatic substituents in hydrosilanes are also presented. The selective bisarylation of bis(hydrosilane)s by directed or non-directed silylation of C-H bonds is also reported herein. Theoretical calculations at the DFT level shed light on the intermediate species in the catalytic cycle and the role played by the ligand system on the Ir(iii)/Ir(i) mechanism. info:eu-repo/grantAgreement/ES/DGA/E07 info:eu-repo/grantAgreement/ES/MEC/FPU14-06003 info:eu-repo/grantAgreement/ES/MICINN-FEDER/CSD2009-00050 info:eu-repo/grantAgreement/ES/MINECO/CTQ2013-42532-P info:eu-repo/grantAgreement/ES/MINECO/CTQ2015-67366-P info:eu-repo/semantics/openAccess by http://creativecommons.org/licenses/by/3.0/es/ 9.063 2017 CHEMISTRY, MULTIDISCIPLINARY 18 / 169 = 0.107 2017 Q1 T1 4.508 2017 Chemistry (miscellaneous) 2017 Q1 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Iglesias, M. (orcid)0000-0003-3144-5320 Munárriz, J. Universidad de Zaragoza (orcid)0000-0001-6089-6126 Polo, V. Universidad de Zaragoza (orcid)0000-0001-5823-7965 Passarelli, V. (orcid)0000-0002-1735-6439 Pérez-Torrente, J.J. Universidad de Zaragoza (orcid)0000-0002-3327-0918 Oro, L.A. Universidad de Zaragoza (orcid)0000-0001-7154-7239 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 2012 755 Universidad de Zaragoza Dpto. Química Física Área Química Física 8, 7 (2017), 4811-4822 Chem. sci. CHEMICAL SCIENCE 2041-6520 1015142 http://zaguan.unizar.es/record/62080/files/texto_completo.pdf Versión publicada 120804 http://zaguan.unizar.es/record/62080/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:62080 articulos driver 2023-09-13-10:40:36 ARTICLE