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Spectroscopie Infrarouge d'Intermédiaires Réactionnels Organométalliques

Abstract : This work is about a new methodology to structurally characterize organometallic reactive intermediates, and more generally molecular ions in the gas phase. Modern ion sources in mass spectrometry enable the transfer of chemical species from solution to the gas phase, and an emerging spectroscopic technique, IRMPD (InfraRed Multiple Photon Dissociation), is used to characterize their structure.
We developed this technique by coupling two mass spectrometers (an ICR ion trap and a Paul type quadrupole ion trap) to the free electron laser located at Orsay. This infrared source is powerful enough to induce a resonant multiple photon absorption, and its tunability in the infrared (700-2000cm-1) was exploited to characterize a large variety of mass selected ions, in particular organometallic species.
Part of this work was dedicated to the optimisation of the two experimental set-ups, as well as to the simulation of IRMPD spectra. We show that those latter are very similar to the infrared absorption spectra calculated with the hybrid density functional B3LYP. We show that IRMPD spectroscopy enables the characterization of the metal spin state and coordination mode for a polydentate ligand in reactive organometallic species that are very difficult to characterize in the condensed phase.
Amine allylation by allylic alcohols, catalysed by palladium complexes, has been investigated. Several catalytic cycles were proposed, and the IRMPD spectra of the observed reactive intermediates allow for their structural characterization and a catalytic cycle is validated.
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Contributor : Luke Macaleese <>
Submitted on : Friday, October 19, 2007 - 8:15:25 PM
Last modification on : Wednesday, September 16, 2020 - 4:32:23 PM


  • HAL Id : tel-00180742, version 1



Luke Macaleese. Spectroscopie Infrarouge d'Intermédiaires Réactionnels Organométalliques. Catalyse. Université Paris Sud - Paris XI, 2006. Français. ⟨tel-00180742⟩



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