Introducing Ion Mobility Mass Spectrometry to Identify Site-Selective C–H Bond Activation in N-Heterocyclic Carbene Metal Complexes
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Otros documentos de la autoría: Mollar Cuni, Andrés; Ibañez-Ibañez, Laura; Guisado-Barrios, Gregorio; Mata Martínez, Jose A; Vicent Barrera, Cristian
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Título
Introducing Ion Mobility Mass Spectrometry to Identify Site-Selective C–H Bond Activation in N-Heterocyclic Carbene Metal ComplexesAutoría
Fecha de publicación
2022-11-14Editor
American Chemical SocietyISSN
1044-0305; 1879-1123Cita bibliográfica
Mollar-Cuni, A., Ibáñez-Ibáñez, L., Guisado-Barrios, G., Mata, J. A., & Vicent, C. (2022). Introducing Ion Mobility Mass Spectrometry to Identify Site-Selective C–H Bond Activation in N-Heterocyclic Carbene Metal Complexes. Journal of the American Society for Mass Spectrometry, 33(12), 2291-2300.Tipo de documento
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info:eu-repo/semantics/acceptedVersionPalabras clave / Materias
Resumen
The activation of C−H bonds in a selective manner
still constitutes a major challenge from a synthetic point of view;
thus, it remains an active area of fundamental and applied research.
Herein, we introduce ion ... [+]
The activation of C−H bonds in a selective manner
still constitutes a major challenge from a synthetic point of view;
thus, it remains an active area of fundamental and applied research.
Herein, we introduce ion mobility spectrometry mass spectrometry-based (IM-MS) approaches to uncover site-selective C−H
bond activation in a series of metal complexes of general formula
[(NHC)LMCl]+ (NHC = N-heterocyclic carbene; L = pentamethylcyclopentadiene (Cp*) or p-cymene; M = Pd, Ru, and Ir).
The C−H bond activation at the N-bound groups of the NHC
ligand is promoted upon collision induced dissociation (CID). The
identification of the resulting [(NHC-H)LM]+ isomers relies on
the distinctive topology that such cyclometalated isomers adopt
upon site-selective C−H bond activation. Such topological
differences can be reliably evidenced as different mobility peaks in their respective CID-IM mass spectra. Alternative isomers are
also identified via dehydrogenation at the Cp*/p-cymene (L) ligands to afford [(NHC)(L-H)M]+
. The fragmentation of the ion
mobility-resolved peaks is also investigated by CID-IM-CID. It enables the assignment of mobility peaks to the specific isomers
formed from C(sp2
)−H or C(sp3
)−H bond activation and distinguishes them from the Cp*/p-cymene (L) dehydrogenation
isomers. The conformational change of the NHC ligands upon C−H bond activation, concomitant with cyclometalation, is also
discussed on the basis of the estimated collision cross section (CCS). A unique conformation change of the pyrene-tagge [-]
Publicado en
J. Am. Soc. Mass Spectrom. 2022, 33, 12, 2291–2300Datos relacionados
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jasms.2c00257Entidad financiadora
Ministerio de Ciencia, Innovación y Universidades | Generalitat Valenciana | Universitat Jaume I | MIU | Gobierno de Aragón | European Union | Universidad de Zaragoza
Código del proyecto o subvención
PID2021-126071OB-C22 | PID2021- 122900NB-I00 | MICIN/AEI/10.13039/ 501100011033/FEDER | PROMETEU/2020/028 | UJI-B2018-23 | FPU20/ 04385 | RYC2019-026693-I/AEI/ 10.13039/501100011033
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Copyright © 2022, American Society for Mass Spectrometry. Published by the American Chemical Society. All rights reserved.
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