Kinetics and mechanisms in gas‐phase ion chemistry by radiolytic methods

Speranza, Maurizio

doi:10.1002/mas.1280110203

Cited by 53 publications

(34 citation statements)

References 150 publications

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“…Appropriate choices of the matrix and solvent strongly increase ion intensities in APTDI. Significantly, atmospheric pressure ionmolecule reactions, which have relied on either radiolysis [10][11][12] or special high-pressure mass spectrometers, [13] now can be studied easily in the atmosphere by using thermally produced ions. Reactions in this pressure regime bridge condensedphase and gas-phase ion chemistry.…”

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confidence: 99%

“…Gas-phase ion chemistry under conditions of very high pressure (0.01 % 10 atm) [12,13] gives kinetic, structural, and stereochemical information which allows meaningful correlations between gas-phase and condensed-phase ion chemistry. [10] To perform atmospheric pressure ion-molecule reactions we generated reactant ions by APTDI in the presence of a neutral reagent in a nitrogen gas stream which served to carry the ion-molecule reaction products into the mass spectrometer.…”

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Thermal Production and Reactions of Organic Ions at Atmospheric Pressure

2006

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Thermal Production and Reactions of Organic Ions at Atmospheric Pressure

2006

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“…Gas-phase ion chemistry under high-pressure conditions established decades ago by Kebarle et al and used to make important thermochemical measurements is now a subject of growing interest [159,[311][312][313] for two reasons. (i) All chemical species encountered along the reaction coordinate are thermally equilibrated with the buffer gas, which allows the observed rate constants of ion/molecule reactions to be interpreted rigorously in terms of candidate mechanisms and potential energy surfaces for that reaction [311,314]; an excellent illustration of this point is provided by the extensively studied S N 2 nucleophilic displacement reaction between chloride and methyl bromide [315,316].…”

Section: High-pressure Ion/molecule Reactionsmentioning

confidence: 99%

Historical Perspectives in the Study of Ion Chemistry by Mass Spectrometry: From the Gas Phase to Solution

Chen

2009

Reactive Intermediates

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Mass spectrometry (MS), originally developing from nineteenth-century physics, has a history dating back more than a hundred years. Since then, the technique has advanced enormously. The advent of new methods of ion production, novel mass analyzers, and new tools for data processing has made it possible to analyze almost all chemical entities, ranging from small organic compounds to large biological molecules and whole living cells/tissues. Today, mass spectrometry has become one of the most powerful and popular modern physical-chemical methods to study the details of elemental and molecular processes in nature. Because of its unparalleled capability of providing information on molecular weight, chemical structures, isotopic content, and even molecular dynamics, mass spectrometry is playing an increasingly significant role in the chemical and life sciences. As a traditional analytical tool and a booming technology for biomedicine, it has found extensive applications in nearly every discipline involving chemical analysis such as petroleum prospecting and refining, food processing, drug discovery, metablomics, genomics, proteomics and structural biology, as well as the environment, public safety, and industrial process monitoring. Along with the development of mass spectrometric technology, the chemistry of gaseous ions has been explored by the study of unimolecular and collision-induced dissociation (CID) [1][2][3][4] and by the study of ion/molecule reactions [2,[5][6][7][8][9][10][11][12][13][14][15][16][17] and ion/ion reactions [18][19][20][21][22][23][24][25][26] in the gas phase. The study of gas-phase ion chemistry has both fundamental and practical significance because it not only provides diverse information on ion reactivity, thermochemistry, and dynamics, but it also forms one basis for chemical analysis using mass spectrometry. In addition, the ion reactivity examined in the isolated gas-phase environment of mass spectrometers has a strong connection with reaction chemistry in solution, as well as contrasting with it. Many important ionic intermediates which are hard to probe in the condensed phase can be easily accessed in the gas phase. Therefore, mass spectrometry has also become an important and unique tool for the mechanistic investigation of organic reactions (particularly organometallic reactions), since soft electrospray ionization (ESI) technology [27, 28] became available. In this regard, there is a large body of work in the literature, which is reviewed in this book. j37This chapter will provide an overview of the history and the current state of the art of mass spectrometry-based study of ion chemistry, specifically of ion/molecule reactions. As this is a broad topic with an immense literature (over 15 000 papers), our emphasis will be placed on the applications of ESI-MS coupled with gas-phase ion/ molecule reactions and tandem mass spectrometry in organometallic chemistry, including probing key intermediates and reaction pathways of organometallic reactions in solution. We will start with...

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“…It is seen that kob is continuously decreased as the concentration of CHCl3 and the degree of clustering of CI-are increased. Under our conditions, kob is expected to be equal to the sum of the individual rate constants, k,, for the reactions of the individual Cl-(CHCIj), ions weighted by the relative abundances, a, (eqs [5][6][7][8], for each ion. The solid curve shown in Figure 11 is a prediction for kob obtained from Kl = 1.41 X los atm-I at 125 OC and by assuming that the rate constants for the reactions of all cluster ions, Cl-(CHC13),z~, with CH3Br are of negligible magnitude relative to that of C1-.…”

Section: (12)mentioning

confidence: 99%

Measurements of equilibria and reactivity of cluster ions at atmospheric pressure: reactions of Cl-(CHCl3)0-2 with methyl bromide and methyl iodide

Giles¹,

Grimsrud²

1993

J. Phys. Chem.

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Measurements by the kinetic ion mobility mass spectrometer (KIMMS) of (i) equilibrium constants for the clustering reactions X-(CHC13)i-l + CHC13 + X-(CHC13)i9 where X-= C1-and Br-and i = 1 or 2, (ii) single ion mobilities for the ions Cl-(CHC1&2 and Br-(CHCl3)0-1, and (iii) rate constants for the s N 2 nucleophilic displacement reactions of a distribution of chloride cluster ions, CI-(CHC13)&2, with CH3Br and with CH31 in nitrogen buffer gas a t atmospheric pressure are reported. A unique feature of the present equilibrium and kinetic measurements is that they are obtained from ion mobility measurements and, therefore, are not subject to potential sources of error that can accompany mass spectrometric-based measurements involving aperture sampling of a high-pressure ion source. Another unique feature of the present investigation is that the reactivity of a selected set of cluster ions is determined under physical conditions in which the individual ions are kinetically labile with respect to cluster decomposition and growth.

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Kinetics and mechanisms in gas‐phase ion chemistry by radiolytic methods

Cited by 53 publications

References 150 publications

Thermal Production and Reactions of Organic Ions at Atmospheric Pressure

Thermal Production and Reactions of Organic Ions at Atmospheric Pressure

Historical Perspectives in the Study of Ion Chemistry by Mass Spectrometry: From the Gas Phase to Solution

Measurements of equilibria and reactivity of cluster ions at atmospheric pressure: reactions of Cl-(CHCl3)0-2 with methyl bromide and methyl iodide

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