doi:10.1039/c5dt02886hengPassarelli, V.Pérez-Torrente, J.J.Oro, L.A.Intramolecular C-H oxidative addition to iridium(i) triggered by trimethyl phosphite in N, N'-diphosphanesilanediamine complexesART-2015-92906The 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.2015http://zaguan.unizar.es/record/4817110.1039/c5dt02886hhttp://zaguan.unizar.es/record/48171oai:zaguan.unizar.es:48171info:eu-repo/grantAgreement/ES/DGA/E07info:eu-repo/grantAgreement/ES/MINECO/CTQ2013-42532-Pinfo:eu-repo/grantAgreement/ES/UZ/CUD2014-CIE-13Dalton Transactions 44, 42 (2015), 18596-18606All rights reservedhttp://www.europeana.eu/rights/rr-f/info:eu-repo/semantics/openAccess