@article{34a63c09f2c1437ba98ddd5f7d6ca480,
title = "Isomerization of a cationic (η5-C5Me5)Ir(III) complex involving remote C–C and C–H bond formation",
abstract = "The reactivity of an unsaturated, cationic (C5Me5)Ir(III) complex (2(Xyl)+) bearing the xylyl-substituted terphenyl phosphine PMe2ArXyl2 (ArXyl2 = C6H3-2,6-(C6H3-2,6-Me2)2) towards triethylamine (NEt3) is studied and compared to our previous investigations based on the related complex 2(Dipp)+ containing the bulkier phosphine PMe2ArDipp2 (ArDipp2 = C6H3-2,6-(C6H3-2,6-iPr2)2). Low-temperature multinuclear NMR studies support the formation of a C–C bond between the deprotonated C5Me5 ligand and a flanking xylyl ring of the phosphine, which becomes dearomatized (complex 4(Xyl)+). Interestingly, this complex presents divergent reactivity relative to the bulkier diisopropylphenyl counterpart, undergoing formal addition of HCl to yield complex 5(Xyl)+, isomeric to the starting complex 2(Xyl)+. These transformations are rationalized by means of Density Functional Theory (DFT) calculations.",
keywords = "C5Me5, DFT, Iridium, Organometallic, Terphenyl phosphine",
author = "Moreno, {Juan Jos{\'e}} and Espada, {Mar{\'i}a F.} and Celia Maya and Jes{\'u}s Campos and Joaqu{\'i}n L{\'o}pez-Serrano and Macgregor, {Stuart A.} and Ernesto Carmona",
note = "Funding Information: This work has been supported by the Spanish Ministry of Economy and Competitiveness/Science (Projects CTQ2016-75193-P [AEI/FEDER,UE] and PID2019-110856GAI00). The use of Computational facilities at the Supercomputing Center of Galicia (CESGA) and theCentro de Servicios de Inform?tica y Redes de Comunicaciones(CSIRC), University of Granada are acknowledged. J.J.M. thanks Junta de Andaluc?a for the postdoctoral program ?Personal Investigador Doctor? (ref. DOC_00153). Funding Information: This work has been supported by the Spanish Ministry of Economy and Competitiveness/Science (Projects CTQ2016-75193-P [AEI/FEDER,UE] and PID2019-110856GAI00). The use of Computational facilities at the Supercomputing Center of Galicia (CESGA) and the Centro de Servicios de Inform{\'a}tica y Redes de Comunicaciones (CSIRC), University of Granada are acknowledged. J.J.M. thanks Junta de Andaluc{\'i}a for the postdoctoral program “Personal Investigador Doctor” (ref. DOC_00153). Publisher Copyright: {\textcopyright} 2021",
year = "2021",
month = jul,
day = "14",
doi = "10.1016/j.poly.2021.115363",
language = "English",
volume = "207",
journal = "Polyhedron",
issn = "0277-5387",
publisher = "Elsevier Limited",
}