Ion mobility mass spectrometry uncovers regioselectivity in the carboxylate-assisted C–H activation of palladium N-heterocyclic carbene complexes
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Other documents of the author: Ibañez-Ibañez, Laura; Mollar Cuni, Andrés; Apaloo-Messan , Edmond; Sharma, Akhilesh Kumar; Mata Martínez, Jose A; Maseras, Feliu; Vicent Barrera, Cristian
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Title
Ion mobility mass spectrometry uncovers regioselectivity in the carboxylate-assisted C–H activation of palladium N-heterocyclic carbene complexesAuthor (s)
Date
2023-11-27Publisher
Royal Society of ChemistryBibliographic citation
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.Type
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Abstract
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. [-]
Funder Name
Ministerio de Ciencia, Innovación y Universidades (Spain) | Universitat Jaume I | MCIN/AEI/10.13039/501100011033 | FEDER | AGAUR
Project code
PID2021-126071OB-C22 | CEX2019-000925-S | PID2020-112825RB-I00 | RED2022-134074-T | UJI-B2022-23 | FPU20/04385 | 2019-BP-00190
Project title or grant
Una manera de hacer Europa
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© 2024 The Royal Society of Chemistry
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