Isomerization of a cationic (η5-C5Me5)Ir(III) complex involving remote C–C and C–H bond formation

Juan José Moreno; María F. Espada; Celia Maya; Jesús Campos; Joaquín López-Serrano; Stuart A. Macgregor; Ernesto Carmona

doi:10.1016/j.poly.2021.115363

Isomerization of a cationic (η⁵-C₅Me₅)Ir(III) complex involving remote C–C and C–H bond formation

Juan José Moreno
, María F. Espada
, Celia Maya
, Jesús Campos
, Joaquín López-Serrano
, Stuart A. Macgregor
, Ernesto Carmona^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

2 Citations (Scopus)

76 Downloads (Pure)

Abstract

The reactivity of an unsaturated, cationic (C₅Me₅)Ir(III) complex (2(Xyl)⁺) bearing the xylyl-substituted terphenyl phosphine PMe₂Ar^Xyl2 (Ar^Xyl2 = 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 PMe₂Ar^Dipp2 (Ar^Dipp2 = 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.

Original language	English
Article number	115363
Journal	Polyhedron
Volume	207
Early online date	14 Jul 2021
DOIs	https://doi.org/10.1016/j.poly.2021.115363
Publication status	Published - 1 Oct 2021

Keywords

C5Me5
DFT
Iridium
Organometallic
Terphenyl phosphine

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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@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 = oct,

day = "1",

doi = "10.1016/j.poly.2021.115363",

language = "English",

volume = "207",

journal = "Polyhedron",

issn = "0277-5387",

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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 - https://www.scopus.com/pages/publications/85111064928

U2 - 10.1016/j.poly.2021.115363

DO - 10.1016/j.poly.2021.115363

M3 - Article

AN - SCOPUS:85111064928

SN - 0277-5387

VL - 207

JO - Polyhedron

JF - Polyhedron

M1 - 115363

ER -