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Unimolecular Dissociation (unimolecular + dissociation)
Selected AbstractsInsertion of Molecular Oxygen in Transition-Metal Hydride Bonds, Oxygen-Bond Activation, and Unimolecular Dissociation of Metal Hydroperoxide Intermediates.HELVETICA CHIMICA ACTA, Issue 3 2008Short Communication Abstract Thermal activation of molecular oxygen is observed for the late-transition-metal cationic complexes [M(H)(OH)]+ with M=Fe, Co, and Ni. Most of the reactions proceed via insertion in a metalhydride bond followed by the dissociation of the resulting metal hydroperoxide intermediate(s) upon losses of O, OH, and H2O. As indicated by labeling studies, the processes for the Ni complex are very specific such that the O-atoms of the neutrals expelled originate almost exclusively from the substrate O2. In comparison to the [M(H)(OH)]+ cations, the ionmolecule reactions of the metal hydride systems [MH]+ (M=Fe, Co, Ni, Pd, and Pt) with dioxygen are rather inefficient, if they occur at all. However, for the solvated complexes [M(H)(H2O)]+ (M=Fe, Co, Ni), the reaction with O2 involving OO bond activation show higher reactivity depending on the transition metal: 60% for the Ni, 16% for the Co, and only 4% for the Fe complex relative to the [Ni(H)(OH)]+/O2 couple. [source] Calculation of Resonances and Product State Distributions for the Unimolecular Dissociation of H2SCHEMINFORM, Issue 39 2002Hong Zhang Abstract For Abstract see ChemInform Abstract in Full Text. [source] Unimolecular dissociation of protonated trans -1,4-diphenyl-2-butene-1,4-dione in the gas phase: rearrangement versus simple cleavageRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 17 2006Lianming Wu Fragmentation mechanisms of trans -1,4-diphenyl-2-butene-1,4-dione were studied using a variety of mass spectrometric techniques. The major fragmentation pathways occur by various rearrangements by loss of H2O, CO, H2O and CO, and CO2. The other fragmentation pathways via simple alpha cleavages were also observed but accounted for the minor dissociation channels in both a two-dimensional (2-D) linear ion trap and a quadrupole time-of-flight (Q-TOF) mass spectrometer. The elimination of CO2 (rather than CH3CHO or C3H8), which was confirmed by an exact mass measurement using the Q-TOF instrument, represented a major fragmentation pathway in the 2-D linear ion trap mass spectrometer. However, the elimination of H2O and CO becomes more competitive in the beam-type Q-TOF instrument. The loss of CO is observed in both the MS2 experiment of m/z 237 and the MS3 experiment of m/z 219 but via the different transition states. The data suggest that the olefinic double bond in protonated trans -1,4-diphenyl-2-butene-1,4-dione plays a key role in stabilizing the rearrangement transition states and increasing the bond dissociation (cleavage) energy to give favorable rearrangement fragmentation pathways. Copyright © 2006 John Wiley & Sons, Ltd. [source] Activation of large lons in FT-ICR mass spectrometryMASS SPECTROMETRY REVIEWS, Issue 2 2005Julia Laskin Abstract The advent of soft ionization techniques, notably electrospray and laser desorption ionization methods, has enabled the extension of mass spectrometric methods to large molecules and molecular complexes. This both greatly extends the applications of mass spectrometry and makes the activation and dissociation of complex ions an integral part of these applications. This review emphasizes the most promising methods for activation and dissociation of complex ions and presents this discussion in the context of general knowledge of reaction kinetics and dynamics largely established for small ions. We then introduce the characteristic differences associated with the higher number of internal degrees of freedom and high density of states associated with molecular complexity. This is reflected primarily in the kinetics of unimolecular dissociation of complex ions, particularly their slow decay and the higher energy content required to induce decomposition,the kinetic shift (KS). The longer trapping time of Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) significantly reduces the KS, which presents several advantages over other methods for the investigation of dissociation of complex molecules. After discussing general principles of reaction dynamics related to collisional activation of ions, we describe conventional ways to achieve single- and multiple-collision activation in FT-ICR MS. Sustained off-resonance irradiation (SORI),the simplest and most robust means of introducing the multiple collision activation process,is discussed in greatest detail. Details of implementation of this technique, required control of experimental parameters, limitations, and examples of very successful application of SORI-CID are described. The advantages of high mass resolving power and the ability to carry out several stages of mass selection and activation intrinsic to FT-ICR MS are demonstrated in several examples. Photodissociation of ions from small molecules can be effected using IR or UV/vis lasers and generally requires tuning lasers to specific wavelengths and/or utilizing high flux, multiphoton excitation to match energy levels in the ion. Photodissociation of complex ions is much easier to accomplish from the basic physics perspective. The quasi-continuum of vibrational states at room temperature makes it very easy to pump relatively large amounts of energy into complex ions and infrared multiphoton dissociation (IRMPD) is a powerful technique for characterizing large ions, particularly biologically relevant molecules. Since both SORI-CID and IRMPD are slow activation methods they have many common characteristics. They are also distinctly different because SORI-CID is intrinsically selective (only ions that have a cyclotron frequency close to the frequency of the excitation field are excited), whereas IRMPD is not (all ions that reside on the optical path of the laser are excited). There are advantages and disadvantages to each technique and in many applications they complement each other. In contrast with these slow activation methods, the less widely appreciated activation method of surface induced dissociation (SID) appears to offer unique advantages because excitation in SID occurs on a sub-picosecond time scale, instantaneously relative to the observation time of any mass spectrometer. Internal energy deposition is quite efficient and readily adjusted by altering the kinetic energy of the impacting ion. The shattering transition,instantaneous decomposition of the ion on the surface,observed at high collision energies enables access to dissociation channels that are not accessible using SORI-CID or IRMPD. Finally, we discuss some approaches for tailoring the surface to achieve particular aims in SID. © 2004 Wiley Periodicals, Inc., Mass Spec Rev 24:135,167, 2005 [source] Fragmentation pathways of 2,3-dimethyl-2,3-dinitrobutane cations in the gas phaseRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 18 2009Martin R. L. Paine 2,3-Dimethyl-2,3-dinitrobutane (DMNB) is an explosive taggant added to plastic explosives during manufacture making them more susceptible to vapour-phase detection systems. In this study, the formation and detection of gas-phase [M+H]+, [M+Li]+, [M+NH4]+ and [M+Na]+ adducts of DMNB was achieved using electrospray ionisation on a triple quadrupole mass spectrometer. The [M+H]+ ion abundance was found to have a strong dependence on ion source temperature, decreasing markedly at source temperatures above 50°C. In contrast, the [M+Na]+ ion demonstrated increasing ion abundance at source temperatures up to 105°C. The relative susceptibility of DMNB adduct ions toward dissociation was investigated by collision-induced dissociation. Probable structures of product ions and mechanisms for unimolecular dissociation have been inferred based on fragmentation patterns from tandem mass (MS/MS) spectra of source-formed ions of normal and isotopically labelled DMNB, and quantum chemical calculations. Both thermal and collisional activation studies suggest that the [M+Na]+ adduct ions are significantly more stable toward dissociation than their protonated analogues and, as a consequence, the former provide attractive targets for detection by contemporary rapid screening methods such as desorption electrospray ionisation mass spectrometry. Copyright © 2009 Commonwealth of Australia. Published by John Wiley & Sons, Ltd. [source] | ||||||||||