IR spectroscopic characterization of intermediates in a gas-phase ionic reaction: The decarbonylation of Co+(acetophenone)

Dunbar, Robert C.; Moore, David T.

doi:10.1016/j.ijms.2007.02.003

Cited by 13 publications

(10 citation statements)

References 24 publications

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“…Furthermore, IRMPD spectroscopy was used to identify the intermediates in the decarbonylation of Co þ (acetophenone). For example, in Figure 2 the IRMPD spectrum reveals that the m/z 151 fragment ion from the reaction of Co þ with acetophenone is Co þ bound to toluene through a cation-p interaction (Dunbar, Moore, & Oomens, 2007a). These particular examples clearly show the potential for spectroscopic studies of ions and ion-molecule complexes in determining structures and confirming mechanistic aspects of ion-molecule reactions.…”

Section: Introductionmentioning

confidence: 89%

Infrared consequence spectroscopy of gaseous protonated and metal ion cationized complexes

Fridgen

2009

Mass Spectrometry Reviews

202

179

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In this article, the new and exciting techniques of infrared consequence spectroscopy (sometimes called action spectroscopy) of gaseous ions are reviewed. These techniques include vibrational predissociation spectroscopy and infrared multiple photon dissociation spectroscopy and they typically complement one another in the systems studied and the information gained. In recent years infrared consequence spectroscopy has provided long-awaited direct evidence into the structures of gaseous ions from organometallic species to strong ionic hydrogen bonded structures to large biomolecules. Much is being learned with respect to the structures of ions without their stabilizing solvent which can be used to better understand the effect of solvent on their structures. This review mainly covers the topics with which the author has been directly involved in research: structures of proton-bound dimers, protonated amino acids and DNA bases, amino acid and DNA bases bound to metal ions and, more recently, solvated ionic complexes. It is hoped that this review reveals the impact that infrared consequence spectroscopy has had on the field of gaseous ion chemistry.

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Section: Introductionmentioning

confidence: 89%

Infrared consequence spectroscopy of gaseous protonated and metal ion cationized complexes

Fridgen

2009

Mass Spectrometry Reviews

202

179

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“…Depending on the cluster size, spectroscopic evidence for a reductive nitrile coupling reaction was found. Reactants and products on a ketone decarbonylation reaction path induced by CO þ for cobalt were spectroscopically characterized by Dunbar, Moore, and Oomens (2007).…”

Section: Ion-molecule Complexes and Metal Clustersmentioning

confidence: 99%

Vibrational spectroscopy of bare and solvated ionic complexes of biological relevance

Polfer

Oomens²

2009

Mass Spectrometry Reviews

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402

393

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The low density of ions in mass spectrometers generally precludes direct infrared (IR) absorption measurements. The IR spectrum of an ion can nonetheless be obtained by inducing photodissociation of the ion using a high-intensity tunable laser. The emergence of free electron lasers (FELs) and recent breakthroughs in bench-top lasers based on nonlinear optics have now made it possible to routinely record IR spectra of gas-phase ions. As the energy of one IR photon is insufficient to cause dissociation of molecules and strongly bound complexes, two main experimental strategies have been developed to effect photodissociation. In infrared multiple-photon dissociation (IR-MPD) many photons are absorbed resonantly and their energy is stored in the bath of vibrational modes, leading to dissociation. In the "messenger" technique a weakly bound van der Waals atom is detached upon absorption of a single photon. Fundamental, historical, and practical aspects of these methods will be presented. Both of these approaches make use of very different methods of ion preparation and manipulation. While in IR-MPD ions are irradiated in trapping mass spectrometers, the "messenger" technique is generally carried out in molecular beam instruments. The main focus of this review is the application of IR spectroscopy to biologically relevant molecular systems (amino acids, peptides, proteins). Particular issues that will be addressed here include gas-phase zwitterions, the (chemical) structures of peptides and their collision-induced dissociation (CID) products, IR spectra of gas-phase proteins, and the chelation of metal-ligand complexes. Another growing area of research is IR spectroscopy on solvated clusters, which offer a bridge between the gas-phase and solution environments. The development of state-of-the-art computational approaches has gone hand-in-hand with advances in experimental techniques. The main advantage of gas-phase cluster research, as opposed to condensed-phase experiments, is that the systems of interest can be understood in detail and structural effects can be studied in isolation. It will be shown that IR spectroscopy of mass-selected (bio)molecular systems is now well-placed to address specific questions on the individual effect of charge carriers (protons and metal ions), as well as solvent molecules on the overall structure.

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“…However the FEL can deliver sufficient pulse energies so that complexes will absorb multiple photons, and are energized to their dissociation threshold [25]. This approach has been used to examine the IR spectra of a number of metal coordination complexes [13,[26][27][28][29][30][31], and has been applied to uranyl coordination complexes in several studies by our group, specifically [UO 2 (solvent) n ] 2+ [32], [UO 2 (solvent)] + [33], [UO 2 (anion)(solvent)] + [34], and [UO 2 (anion) 3 ] − complexes [35,36]. These measurements have provided a quantitative basis for evaluating the effects of the number of ligands, and ligand nucleophilicity on binding within the complexes, and have provided a useful basis for comparing the results of theoretical calculations.…”

Section: Introductionmentioning

confidence: 99%

Vibrational spectra of discrete UO22+ halide complexes in the gas phase

Groenewold

Stipdonk

Jong

et al. 2010

International Journal of Mass Spectrometry

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IR spectroscopic characterization of intermediates in a gas-phase ionic reaction: The decarbonylation of Co+(acetophenone)

Cited by 13 publications

References 24 publications

Infrared consequence spectroscopy of gaseous protonated and metal ion cationized complexes

Infrared consequence spectroscopy of gaseous protonated and metal ion cationized complexes

Vibrational spectroscopy of bare and solvated ionic complexes of biological relevance

Vibrational spectra of discrete UO22+ halide complexes in the gas phase

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