Rhodium(i) complexes with proton-responsive anionic tethered N-heterocyclic carbene ligands: synthesis and application in alkyne dimerization

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dc.contributor.authorKaratas, Mert Olgun
dc.contributor.authorHinojosa, Diego R.
dc.contributor.authorPassarelli, Vincenzo
dc.contributor.authorOro, Luis A.
dc.contributor.authorPerez-Torrente, Jesus J.
dc.contributor.authorCastarlenas, Ricardo
dc.date.accessioned2026-04-04T13:34:40Z
dc.date.available2026-04-04T13:34:40Z
dc.date.issued2025
dc.departmentİnönü Üniversitesi
dc.description.abstractA series of rhodium(i) complexes of formula Rh{kappa 2C,X-(IDippR)}(cod) and Rh{kappa 2C,X-(IDippR)}(CO)2 {IDippR = 1-(R)-3-(2,6-diisopropylphenyl)-imidazolin-2-carbene; X = N, O; R = (6-yl-2-pyridone), (CH2CH2NC( 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 O)Ph), (CH2CH2COO); (cod = 1,5-cyclooctadiene)} containing anionic-tethered NHC-functionalized ligands, including pyridonato, amidato or carboxylato groups at the N-wingtip, has been prepared and their application to alkyne homocoupling has been investigated. The chelate coordination of the NHC-functionalized ligand generates 5, 6 and 7-membered metallacycles for pyridonato, amidato and carboxylato substituents, respectively. Preparation of the mixed bis-NHC derivative Rh{kappa 2C,O-(IDippCarbx)}(CO)(IPr) {IPr = 1,3-bis-(2,6-diisopropylphenyl)-imidazolin-2-carbene} is possible due to lability of one of the CO ligands in the bis-CO precursor. Reversible protonation is observed for pyridonato and carboxylato moieties but not for amidato counterpart. Alkyne dimerization catalytic activity is reported for N-based anionic groups whereas carboxylato counterparts are inefficient. A proton transfer mechanism is invoked for the gem-selectivity observed for cod-based catalysts whereas alkyne insertion is the regioselectivity-determining step for CO-containing analogues.
dc.description.sponsorshipSpanish Ministerio de Ciencia, Innovacion y Universidades MICIU/AEI/ [PID2019-103965GB-I00, PID2022-137208NB-I00]; Departamento de Ciencia, Universidad y Sociedad del Conocimiento del Gobierno de Aragon [E42_23R]; Departamento de Ciencia, Universidad y Sociedad del Conocimiento del Gobierno de Aragn
dc.description.sponsorshipFinancial support from the Spanish Ministerio de Ciencia, Innovacion y Universidades MICIU/AEI/10.13039/501100011033, under the Projects PID2019-103965GB-I00 and PID2022-137208NB-I00, and the Departamento de Ciencia, Universidad y Sociedad del Conocimiento del Gobierno de Aragon (group E42_23R) is gratefully acknowledged. MOK thankfully acknowledge the University of Zaragoza for a contract under the program Researchers Affected by Natural Disasters. The use of the Servicio General de Apoyo a la Investigacion-SAI of the University of Zaragoza, and the scientific-technical services of the ISQCH/CEQMA (CSIC) is gratefully acknowledged.
dc.identifier.doi10.1039/d5dt01516b
dc.identifier.endpage15319
dc.identifier.issn1477-9226
dc.identifier.issn1477-9234
dc.identifier.issue40
dc.identifier.orcid0000-0002-1735-6439
dc.identifier.orcid0000-0002-4849-2062
dc.identifier.orcid0000-0003-4460-8678
dc.identifier.orcid0000-0002-3327-0918
dc.identifier.orcid0000-0001-8500-2088
dc.identifier.pmid40994186
dc.identifier.scopus2-s2.0-105018683319
dc.identifier.scopusqualityQ2
dc.identifier.startpage15306
dc.identifier.urihttps://doi.org/10.1039/d5dt01516b
dc.identifier.urihttps://hdl.handle.net/11616/109312
dc.identifier.volume54
dc.identifier.wosWOS:001578191900001
dc.identifier.wosqualityQ1
dc.indekslendigikaynakWeb of Science
dc.indekslendigikaynakScopus
dc.indekslendigikaynakPubMed
dc.language.isoen
dc.publisherRoyal Soc Chemistry
dc.relation.ispartofDalton Transactions
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanı
dc.rightsinfo:eu-repo/semantics/closedAccess
dc.snmzKA_WOS_20250329
dc.subjectTo-Tail Dimerization
dc.subjectTerminal Alkynes
dc.subjectMetal-Complexes
dc.subjectNhc Ligands
dc.subjectCatalysts
dc.subjectIridium
dc.subjectBond
dc.subjectReactivity
dc.subjectCarbopalladation
dc.subjectHydrogenation
dc.titleRhodium(i) complexes with proton-responsive anionic tethered N-heterocyclic carbene ligands: synthesis and application in alkyne dimerization
dc.typeArticle

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