Ion mobility mass spectrometry uncovers regioselectivity in the carboxylate-assisted C–H activation of palladium N-heterocyclic carbene complexes
Impacto
Scholar |
Otros documentos de la autoría: Ibañez-Ibañez, Laura; Mollar Cuni, Andrés; Apaloo-Messan , Edmond; Sharma, Akhilesh Kumar; Mata Martínez, Jose A; Maseras, Feliu; Vicent Barrera, Cristian
Metadatos
Mostrar el registro completo del ítemcomunitat-uji-handle:10234/9
comunitat-uji-handle2:10234/160292
comunitat-uji-handle3:10234/160293
comunitat-uji-handle4:
INVESTIGACIONMetadatos
Título
Ion mobility mass spectrometry uncovers regioselectivity in the carboxylate-assisted C–H activation of palladium N-heterocyclic carbene complexesAutoría
Fecha de publicación
2023-11-27Editor
Royal Society of ChemistryCita bibliográfica
IBÁÑEZ-IBÁÑEZ, Laura, et al. Ion mobility mass spectrometry uncovers regioselectivity in the carboxylate-assisted C–H activation of palladium N-heterocyclic carbene complexes. Dalton Transactions, 2024, vol. 53, no 2, p. 656-665.Tipo de documento
info:eu-repo/semantics/articleVersión
info:eu-repo/semantics/acceptedVersionPalabras clave / Materias
Resumen
Carboxylate-assisted Pd-catalyzed C–H bond activation constitutes a mild and versatile synthetic tool to efficiently and selectively cleave inert C–H bonds. Herein, we demonstrate a simple method to experimentally ... [+]
Carboxylate-assisted Pd-catalyzed C–H bond activation constitutes a mild and versatile synthetic tool to efficiently and selectively cleave inert C–H bonds. Herein, we demonstrate a simple method to experimentally evaluate both reactivity and selectivity in such systems using mass spectrometry (MS) methods. The N-heterocyclic carbene (NHC) cations [(NHC)PdX]+, bearing as X− ligand bases commonly used to promote the C–H activation (carboxylates and bicarbonate), are generated in the gas-phase by ESI-MS. Their C–H bond activation at the N-bound groups of the NHC is then studied using Collision Induced Dissociation (CID) experiments. Ion Mobility Spectrometry (IM)-MS is exploited to identify a number of regioisomers associated with the distinctive site selective C–H activations. It is demonstrated that such C–H activation concomitant with acetic acid release occurs from a mixture of activated [(NHC-H)Pd(CH3CO2H)]+ and non-activated [(NHC)Pd(CH3CO2)]+ complexes. The identity of the X-type ligands (X = Cl−, carboxylates and bicarbonate) has a significant impact on the regioisomer branching ratio upon CID conditions. IM-MS in conjunction with a DFT mechanistic study is presented for the acetate-assisted C–H activation of the [(NHC)Pd(CH3CO2)]+ cation featuring butyl and aryl as N-donor groups. [-]
Entidad financiadora
Ministerio de Ciencia, Innovación y Universidades (Spain) | Universitat Jaume I | MCIN/AEI/10.13039/501100011033 | FEDER | AGAUR
Código del proyecto o subvención
PID2021-126071OB-C22 | CEX2019-000925-S | PID2020-112825RB-I00 | RED2022-134074-T | UJI-B2022-23 | FPU20/04385 | 2019-BP-00190
Título del proyecto o subvención
Una manera de hacer Europa
Derechos de acceso
© 2024 The Royal Society of Chemistry
http://rightsstatements.org/vocab/InC/1.0/
info:eu-repo/semantics/embargoedAccess
http://rightsstatements.org/vocab/InC/1.0/
info:eu-repo/semantics/embargoedAccess
Aparece en las colecciones
- INAM_Articles [506]