A pulsed ionization high-pressure mass spectrometric study of methyl cation transfer and methyl cation-induced clustering in dimethyl ether-acetone mixtures

Szulejko, Jan E.; Fisher, J.J.; McMahon, T. B.; Wronka, John

doi:10.1016/0168-1176(88)80092-2

Cited by 46 publications

(38 citation statements)

References 22 publications

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“…For Eqs. (40) and (41) reaction is clearly observable. The occurrence of rotations in ion-molecule clusters to facilitate isomerization is not uncommon.…”

Section: Potential Energy Surfacesmentioning

confidence: 89%

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Thermochemistry and structures of solvated SN2 complexes and transition states in the gas phase: experiment and theory

Bogdanov

McMahon

2005

International Journal of Mass Spectrometry

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“…For Eqs. (40) and (41) reaction is clearly observable. The occurrence of rotations in ion-molecule clusters to facilitate isomerization is not uncommon.…”

Section: Potential Energy Surfacesmentioning

confidence: 89%

“…The instrument, constructed at the University of Waterloo, has been described in detail previously [40].…”

Section: Methodsmentioning

confidence: 99%

Thermochemistry and structures of solvated SN2 complexes and transition states in the gas phase: experiment and theory

Bogdanov

McMahon

2005

International Journal of Mass Spectrometry

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“…Previous examples 38,39 from this laboratory clearly illustrate how powerful this technique is and how with careful experimental work it has become possible to observe isomeric forms of ionic species in the gas phase relatively frequently using PHPMS.…”

Section: Introductionmentioning

confidence: 96%

Intramolecular Solvation of Carboxylate Anions in the Gas Phase

Norrman

McMahon

1999

J. Phys. Chem. A

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Proton exchange reactions between acetate, n-butanoate, 2-ethylhexanoate, and n-decanoate were studied experimentally by the use of PHPMS and theoretically by the use of ab initio methods. The occurrence of a curvature in some of the van't Hoff plots suggests isomerization of at least one of the participants in the equilibrium. This isomerization is suggested to be an intramolecular solvation of the carboxylate anions via unconventional hydrogen bonding. These interactions are discussed in terms of charge distributions in the unfolded and folded conformers of the carboxylates. Thermochemical values for the intramolecular solvation were deconvoluted from the curved van't Hoff plots by a fitting procedure. The thermochemical data for the intramolecular solvation was used to calculate the conformer composition of the carboxylate anions. Various properties related to the intramolecular solvation of the carboxylate anions are discussed.

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“…The crucial step in this process involves an alkyl group migration from oxonium cation to one of the nucleophilic centers of the radical within INC. The ability of oxonium ions to act as an alkylating agent towards the appropriate nucleophilic sites in the gas phase is well known; 2,3 however, only in the paper by Tu and Holmes 4 was a reaction mechanism similar to that proposed by us depicted. Such an alkyl group migration reactions proceeding via an INC are still only weakly recognized, although the INC-mediated mechanisms themselves have been studied in depth, mainly in connection with the transfer of hydrogen atoms.…”

Section: Introductionmentioning

confidence: 75%

Similarities and differences in the electron ionization‐induced fragmentation of structurally related N‐alkoxymethyl lactams and sultams

Szmigielski

Danikiewicz

2005

J. Mass Spectrom.

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Unimolecular fragmentation patterns of the molecular ions of selected lactams and sultams bearing alkoxymethyl group at the nitrogen atom were studied. The main common fragmentation reaction observed for all compounds studied in this work is the elimination of an aldehyde molecule. This reaction is considered to proceed via two different mechanisms. For lactams, hydrogen rearrangement within an alkoxymethyl group is observed, which leads to the appropriate N-methyl derivatives. For sultams, transfer of the methyl group to the nitrogen and oxygen atoms, proceeding through an ion-neutral complex, dominates. Another important fragmentation channel characteristic exclusively for lactams is the loss of an alkyl radical. This process takes place within the N-alkoxymethyl moiety, yielding the appropriate protonated ion of N-formyllactams. This process is accompanied by relatively high kinetic energy release.

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A pulsed ionization high-pressure mass spectrometric study of methyl cation transfer and methyl cation-induced clustering in dimethyl ether-acetone mixtures

Cited by 46 publications

References 22 publications

Thermochemistry and structures of solvated SN2 complexes and transition states in the gas phase: experiment and theory

Thermochemistry and structures of solvated SN2 complexes and transition states in the gas phase: experiment and theory

Intramolecular Solvation of Carboxylate Anions in the Gas Phase

Similarities and differences in the electron ionization‐induced fragmentation of structurally related N‐alkoxymethyl lactams and sultams

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