48171 20210121114511.0 doi 10.1039/c5dt02886h sideral 92906 ART-2015-92906 eng (orcid)0000-0002-1735-6439 Passarelli, V. Intramolecular C-H oxidative addition to iridium(i) triggered by trimethyl phosphite in N, N'-diphosphanesilanediamine complexes 2015 Access copy available to the general public Unrestricted The reaction of Ir(SiNP)(cod)]PF6] (1]PF6]) and of IrCl(SiNP)(cod) (5) (SiNP = SiMe2{N(4-C6H4CH3)PPh2}2) with trimethyl phosphite affords the iridium(iii) derivatives of the formula IrHClx(SiNP-H){P(OMe)3}2-x](1-x)+ (x = 0, 3+; x = 1, 6) containing the ¿3C, P, P'-coordinated SiNP-H ligand (SiNP-H = Si(CH2)(CH3){N(4-C6H4CH3)PPh2}2). The thermally unstable pentacoordinated cation Ir(SiNP){P(OMe)3}(cod)]+ (2+) has been detected as an intermediate of the reaction and has been fully characterised in solution. Also, the mechanism of the C-H oxidative addition has been elucidated by DFT calculations showing that the square planar iridium(i) complexes of the formula IrClx(SiNP){P(OMe)3}2-x](1-x)+ (x = 0, 4+; x = 1, 7) should be firstly obtained from 2+ and finally should undergo the C-H oxidative addition to iridium(i) via a concerted intramolecular mechanism. The influence of the counterion of 2+ on the outcome of the C-H oxidative addition reaction has also been investigated. info:eu-repo/grantAgreement/ES/DGA/E07 info:eu-repo/grantAgreement/ES/MINECO/CTQ2013-42532-P info:eu-repo/grantAgreement/ES/UZ/CUD2014-CIE-13 info:eu-repo/semantics/openAccess All rights reserved http://www.europeana.eu/rights/rr-f/ 4.177 2015 CHEMISTRY, INORGANIC & NUCLEAR 10 / 46 = 0.217 2015 Q1 T1 1.302 2015 Inorganic Chemistry 2015 Q1 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion (orcid)0000-0002-3327-0918 Pérez-Torrente, J.J. Universidad de Zaragoza (orcid)0000-0001-7154-7239 Oro, L.A. Universidad de Zaragoza 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 44, 42 (2015), 18596-18606 Dalton Trans. Dalton Transactions 1477-9226 2285765 http://zaguan.unizar.es/record/48171/files/texto_completo.pdf Versión publicada 95080 http://zaguan.unizar.es/record/48171/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:48171 articulos driver 2021-01-21-10:57:27 ARTICLE