125871 20240319080950.0 doi 10.1039/d2dt00794k sideral 128809 ART-2022-128809 eng Palmese, M. Universidad de Zaragoza Synthesis and reactivity of an iridium complex based on a tridentate aminophosphano ligand 2022 Access copy available to the general public Unrestricted The iridium(iii) hydride compound IrH{¿3C, P, P'-(SiNP-H)}(CNtBu)2]PF6] (1PF6) was obtained by reaction of Ir(SiNP)(cod)]PF6] with CNtBu as the result of the intramolecular oxidative addition of the SiCH2-H bond to iridium(i) SiNP = Si(CH3)2{N(4-tolyl)PPh2}2, SiNP-H = CH2Si(CH3){N(4-tolyl)PPh2}2]. The mechanism of the reaction was investigated by NMR spectroscopy and DFT calculations showing that the pentacoordinated intermediate Ir(SiNP)(cod)(CNtBu)]PF6] (2PF6) forms in the first place and that further reacts with CNtBu, affording the square planar intermediate Ir(SiNP)(CNtBu)2]PF6] (3PF6) that finally undergoes the intramolecular oxidative addition of the SiCH2-H bond. The reactivity of 1PF6 was investigated. On one hand, the reaction of 1PF6 with N-chlorosuccinimide or N-bromosuccinimide provides the haloderivatives IrX{¿3C, P, P'-(SiNP-H)}(CNtBu)2]PF6] (X = Cl, 4PF6; Br, 5PF6), and the reaction of 5PF6 with AgPF6 in the presence of acetonitrile affords the solvato species Ir{¿3C, P, P'-(SiNP-H)}(CH3CN)(CNtBu)2]2+ (62+) isolated as the hexafluorophosphate salt. On the other hand, the reaction of 1PF6 with HBF4 gives the iridium(iii) compound IrH(CH2SiF2CH3)(HNP)2(CNtBu)2]BF4] (7BF4) as the result of the formal addition of hydrogen fluoride to the Si-N bonds of 1+ HNP = HN(4-tolyl)PPh2]. A similar outcome was observed in the reaction of 1PF6 with CF3COOH rendering 7PO2F2. In this case the intermediate IrH{¿2C, P-CH2SiMeFN(4-tolyl)PPh2}(HNP)(CNtBu)2]+ (8+) was observed and characterised in situ by NMR spectroscopy. DFT calculations suggests that the reaction goes through the sequential protonation of the nitrogen atom of the Si-N-P moiety followed by the formal addition of fluoride ion to silicon. Also, the crystal structures of SiNP, 1PF6, 4PF6 and 7BF4 have been determined by X-ray diffraction measurements. © 2022 The Royal Society of Chemistry info:eu-repo/grantAgreement/ES/DGA-FSE/E42-20R info:eu-repo/grantAgreement/ES/MICINN/PID2019-103965GB-I00/AEI/10.13039/501100011033 info:eu-repo/semantics/openAccess by http://creativecommons.org/licenses/by/3.0/es/ 4.0 2022 CHEMISTRY, INORGANIC & NUCLEAR 7 / 42 = 0.167 2022 Q1 T1 0.79 2022 Inorganic Chemistry 2022 Q1 7.1 2022 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion Pérez-Torrente, J. J. Universidad de Zaragoza (orcid)0000-0002-3327-0918 Passarelli, V. (orcid)0000-0002-1735-6439 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 51 (2022), 7142 - 7153 Dalton Trans. Dalton Transactions 1477-9226 1105707 http://zaguan.unizar.es/record/125871/files/texto_completo.pdf Postprint 2204835 http://zaguan.unizar.es/record/125871/files/texto_completo.jpg?subformat=icon icon Postprint oai:zaguan.unizar.es:125871 articulos driver 2024-03-18-12:58:15 ARTICLE