TY - JOUR
T1 - Isomerization of a cationic (η5-C5Me5)Ir(III) complex involving remote C–C and C–H bond formation
AU - Moreno, Juan José
AU - Espada, María F.
AU - Maya, Celia
AU - Campos, Jesús
AU - López-Serrano, Joaquín
AU - Macgregor, Stuart A.
AU - Carmona, Ernesto
N1 - 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 Informática y Redes de Comunicaciones (CSIRC), University of Granada are acknowledged. J.J.M. thanks Junta de Andalucía for the postdoctoral program “Personal Investigador Doctor” (ref. DOC_00153).
Publisher Copyright:
© 2021
PY - 2021/10/1
Y1 - 2021/10/1
N2 - 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.
AB - 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.
KW - C5Me5
KW - DFT
KW - Iridium
KW - Organometallic
KW - Terphenyl phosphine
UR - http://www.scopus.com/inward/record.url?scp=85111064928&partnerID=8YFLogxK
U2 - 10.1016/j.poly.2021.115363
DO - 10.1016/j.poly.2021.115363
M3 - Article
AN - SCOPUS:85111064928
VL - 207
JO - Polyhedron
JF - Polyhedron
SN - 0277-5387
M1 - 115363
ER -