Gas-Phase Basicity and Heat of Formation of Sulfine CH<sub>2</sub>SO

Bouchoux, Guy; Salpin, Jean‐Yves

doi:10.1021/ja9610601

Cited by 41 publications

(23 citation statements)

References 18 publications

(23 reference statements)

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“…191 In both the equilibrium and bracketing methods, a proton is transferred from a monocation, MH C , to a neutral base species, B, with known gas-phase basicity, according to the Reaction (2.2). The free-energy change for this reaction, G rxn , is the difference in gas-phase basicities of M and B, 196,197 Other tools, such as triple-quadrupole instruments, 198 quadrupole ion traps 199,200 and guided ion beam mass spectrometers, 201 have also been employed. 'Flow reactor' or 'flow tube' techniques, including flowing afterglow (FA) and selected ion flow drift tube (SIFDT), have been used for the determination of thermodynamic values associated with proton transfer.…”

Section: Reaction (22) Ion-molecule Proton Transfer: Mh + + B → M +mentioning

confidence: 99%

“…'Flow reactor' or 'flow tube' techniques, including flowing afterglow (FA) and selected ion flow drift tube (SIFDT), have been used for the determination of thermodynamic values associated with proton transfer. 193,202 As one of the most widely studied types of ion-molecule reactions in the gas phase, studies involving this reaction have provided a substantial database of thermochemical information for organic compounds, 197,199,203 monosaccharides, 204 terpenes, 198 multidentate ligands 205 and biomolecules. Proton transfer reactions between multiply protonated species and neutral bases have been studied using a variety of mass spectrometric techniques including ion trapping approaches based on the quadrupole ion trap 207 -209 and FT-ICR tandem mass spectrometry.…”

Section: Reaction (22) Ion-molecule Proton Transfer: Mh + + B → M +mentioning

confidence: 99%

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Charge permutation reactions in tandem mass spectrometry

McLuckey

2004

J. Mass Spectrom.

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Central to the tandem mass spectrometry experiment is the process that gives rise to product ions, i.e. the reaction intermediate to stages of mass analysis. Changes in mass or charge of the parent ion (or both) are generally readily detected by all forms of tandem mass spectrometry. Charge changing, or charge permutation, reactions have a long history in mass spectrometry. However, with the advent of new ionization methods, such as electrospray ionization, and the expansion of tandem mass spectrometry instrumentation to include ion trapping instruments, the past decade has seen a major increase in the types of charge permutation reactions that can be studied. Most charge permutation reactions involve electrons or protons as the charge mediating agents. This report, therefore, provides an overview of charge permutation reactions involving protons or electrons. Particular emphasis is placed on processes that involve interactions of precursor ions with gaseous neutral species, electrons or oppositely charged ions. Charge permutation reactions involving electron gain/loss are described first according to a rough order of the energy required for the reaction beginning with the most endoergic reactions and ending with the most exoergic reactions. An analogous approach is then taken with charge permutation reactions involving proton gain/loss. Important charge permutation reactions discussed herein, among others, include those referred to as charge inversion, charge stripping, electron capture dissociation, collision-induced ionization and charge separation. These reaction types, and others described herein, are the subjects of active research and are also finding use in many current areas of application.

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Section: Reaction (22) Ion-molecule Proton Transfer: Mh + + B → M +mentioning

confidence: 99%

Section: Reaction (22) Ion-molecule Proton Transfer: Mh + + B → M +mentioning

confidence: 99%

Charge permutation reactions in tandem mass spectrometry

McLuckey

2004

J. Mass Spectrom.

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“…This point has been treated by Hunter and Lias 1 by considering the GB(M) values obtained by the thermokinetic method 'as if they were bracketed by the GB values of the nearest bases below and above that of M' in the sets of experiments reported in our original publications. The thermokinetic data of ketene, 4 methylketene, 4 formaldimine, 4 vinylimine 5 and sulfine 6 have been processed in this way. From a general point of view, the above mentioned approximation is dependent on the range of reaction efficiency (RE) covered by the bases B involved in reaction (1).…”

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confidence: 99%

Re-evaluated gas phase basicity and proton affinity data from the thermokinetic method

Bouchoux

Salpin

1999

Rapid Commun. Mass Spectrom.

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Received 15 February 1999; Revised 22 March 1999; Accepted 23 March 1999 Gas phase basicities (GB) and proton affinities (PA) of molecules are still the subject of active experimental and theoretical investigations. Recently, a formidable compilation of evaluated GB and PA values of ca. 1700 neutrals has appeared (the Hunter and Lias compilation, 1 which will be abreviated HL hereafter), expanding and correcting the previous review established by the same laboratory.2 Reevaluation of the GB/PA values derived from gas phase equilibrium experiments or from the 'kinetic method' has been made in a more or less straightforward manner.1 For the values obtained by the 'thermokinetic method' the corrections have been made by using a bracketing estimate from the original data. The goal of the present note is to examine, in a more elaborate way, the impact of the new standard values on the GB and PA values obtained in the first applications of the thermokinetic method.It may be briefly recalled that the 'thermokinetic' method of determination of gas basicity and proton affinity values uses a correlation between the reaction efficiency (RE) and the standard free energy change, DG o , or the standard enthalpy variation, DH o , of a proton transfer process. 3 For a reaction of the type (1):the expected correlation is expressed as Eqn. 2:where k exp and k coll are the experimental and collision rate coefficients, respectively, DG In a similar way PA(M) can be deduced from a correlation between the reaction efficiency of reaction (1) and PA(B) (Eqn. 5): In fact, as recognized by Hunter and Lias, 1 a correct re-evaluation of the thermokinetic GB or PA values needs a new fitting of the experimental data. The aim of the present paper is to provide the result of a true thermokinetic treatment of the data from Refs 4-6 using the new HL values (noted GB HL and PA HL ) for the reference

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“…Benson [5] estimated the sul®ne heat of formation (DH°f) to be À51 AE 22 kJ/mol. A recent Fourier transform-ion cyclotron resonance (FT-ICR) experiment, on the basis of the Dr f of CH 2 SOH , proposed a new value of À8 AE 10 kJ/mol at 298 K [6]. A similar value was obtained theoretically at the CAS-SDCI level (À9 AE 14 kJ/mol at 298 K) while standard G2 and G2(MP2) calculations gave À18 and À30 kJ/mol, respectively, at 0 K [7].…”

Section: Introductionmentioning

confidence: 99%

“…Proton anity (PA) and gas-phase basicity (GB) were ®rst obtained through an FT-ICR experiment [6]. The suggested values are PA = 786 kJ/mol and GB = 758 kJ/mol [6].…”

Section: Introductionmentioning

confidence: 99%

Gas-phase properties and Fukui indices of sulfine (CH 2 SO). Potential energy surface and maximum hardness principle for its protonation process. A density functional study

Mineva

Russo

Sicilia

et al. 1999

Theoretical Chemistry Accounts: Theory, Computation, and Modeli

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Gas-phase thermochemical properties of sul®ne CH 2 SO and the potential energy surface of its protonation process were studied by the density functional method employing dierent exchange-correlation potentials. All calculations showed that the most stable protonated isomer is planar with the proton bonded to the oxygen atom in a trans arrangement of the skeleton. Three transition states were located that allow interconversion between the dierent isomers. Hardnesses and Fukui indices were calculated to follow the reactivity trend along the protonation path and to explain the preference for a particular protonation site on neutral sul®ne. Proton anity, gas-phase basicity and heat of formation values, obtained for the ®rst time fully quantum mechanically, agree well with those derived by a recent mass spectrometry experimental study. Good agreement between density functional theory and previous high-level theoretical and experimental data was also found for the heat of formation of sul®ne and its most stable protonated form.

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Gas-Phase Basicity and Heat of Formation of Sulfine CH₂SO

Cited by 41 publications

References 18 publications

Charge permutation reactions in tandem mass spectrometry

Charge permutation reactions in tandem mass spectrometry

Re-evaluated gas phase basicity and proton affinity data from the thermokinetic method

Gas-phase properties and Fukui indices of sulfine (CH 2 SO). Potential energy surface and maximum hardness principle for its protonation process. A density functional study

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Gas-Phase Basicity and Heat of Formation of Sulfine CH2SO

Cited by 41 publications

References 18 publications

Charge permutation reactions in tandem mass spectrometry

Charge permutation reactions in tandem mass spectrometry

Re-evaluated gas phase basicity and proton affinity data from the thermokinetic method

Gas-phase properties and Fukui indices of sulfine (CH 2 SO). Potential energy surface and maximum hardness principle for its protonation process. A density functional study

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Gas-Phase Basicity and Heat of Formation of Sulfine CH₂SO