000125871 001__ 125871
000125871 005__ 20240319080950.0
000125871 0247_ $$2doi$$a10.1039/d2dt00794k
000125871 0248_ $$2sideral$$a128809
000125871 037__ $$aART-2022-128809
000125871 041__ $$aeng
000125871 100__ $$aPalmese, M.$$uUniversidad de Zaragoza
000125871 245__ $$aSynthesis and reactivity of an iridium complex based on a tridentate aminophosphano ligand
000125871 260__ $$c2022
000125871 5060_ $$aAccess copy available to the general public$$fUnrestricted
000125871 5203_ $$aThe iridium(iii) hydride compound IrH{¿3C, P, P'-(SiNP-H)}(CNtBu)2]PF6] (1PF6) was obtained by reaction of Ir(SiNP)(cod)]PF6] with CNtBu as the result of the intramolecular oxidative addition of the SiCH2-H bond to iridium(i) SiNP = Si(CH3)2{N(4-tolyl)PPh2}2, SiNP-H = CH2Si(CH3){N(4-tolyl)PPh2}2]. The mechanism of the reaction was investigated by NMR spectroscopy and DFT calculations showing that the pentacoordinated intermediate Ir(SiNP)(cod)(CNtBu)]PF6] (2PF6) forms in the first place and that further reacts with CNtBu, affording the square planar intermediate Ir(SiNP)(CNtBu)2]PF6] (3PF6) that finally undergoes the intramolecular oxidative addition of the SiCH2-H bond. The reactivity of 1PF6 was investigated. On one hand, the reaction of 1PF6 with N-chlorosuccinimide or N-bromosuccinimide provides the haloderivatives IrX{¿3C, P, P'-(SiNP-H)}(CNtBu)2]PF6] (X = Cl, 4PF6; Br, 5PF6), and the reaction of 5PF6 with AgPF6 in the presence of acetonitrile affords the solvato species Ir{¿3C, P, P'-(SiNP-H)}(CH3CN)(CNtBu)2]2+ (62+) isolated as the hexafluorophosphate salt. On the other hand, the reaction of 1PF6 with HBF4 gives the iridium(iii) compound IrH(CH2SiF2CH3)(HNP)2(CNtBu)2]BF4] (7BF4) as the result of the formal addition of hydrogen fluoride to the Si-N bonds of 1+ HNP = HN(4-tolyl)PPh2]. A similar outcome was observed in the reaction of 1PF6 with CF3COOH rendering 7PO2F2. In this case the intermediate IrH{¿2C, P-CH2SiMeFN(4-tolyl)PPh2}(HNP)(CNtBu)2]+ (8+) was observed and characterised in situ by NMR spectroscopy. DFT calculations suggests that the reaction goes through the sequential protonation of the nitrogen atom of the Si-N-P moiety followed by the formal addition of fluoride ion to silicon. Also, the crystal structures of SiNP, 1PF6, 4PF6 and 7BF4 have been determined by X-ray diffraction measurements. © 2022 The Royal Society of Chemistry
000125871 536__ $$9info:eu-repo/grantAgreement/ES/DGA-FSE/E42-20R$$9info:eu-repo/grantAgreement/ES/MICINN/PID2019-103965GB-I00/AEI/10.13039/501100011033
000125871 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttp://creativecommons.org/licenses/by/3.0/es/
000125871 590__ $$a4.0$$b2022
000125871 592__ $$a0.79$$b2022
000125871 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b7 / 42 = 0.167$$c2022$$dQ1$$eT1
000125871 593__ $$aInorganic Chemistry$$c2022$$dQ1
000125871 594__ $$a7.1$$b2022
000125871 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000125871 700__ $$0(orcid)0000-0002-3327-0918$$aPérez-Torrente, J. J.$$uUniversidad de Zaragoza
000125871 700__ $$0(orcid)0000-0002-1735-6439$$aPassarelli, V.
000125871 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000125871 773__ $$g51 (2022), 7142 - 7153$$pDalton Trans.$$tDalton Transactions$$x1477-9226
000125871 8564_ $$s1105707$$uhttps://zaguan.unizar.es/record/125871/files/texto_completo.pdf$$yPostprint
000125871 8564_ $$s2204835$$uhttps://zaguan.unizar.es/record/125871/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000125871 909CO $$ooai:zaguan.unizar.es:125871$$particulos$$pdriver
000125871 951__ $$a2024-03-18-12:58:15
000125871 980__ $$aARTICLE