Competing rearrangement reactions in small gas-phase ionic complexes: The internal SN2 and nitro-nitrite rearrangements in nitroalkane proton-bound pairs

Poon, Clement; Mayer, Paul M.

doi:10.1016/j.ijms.2006.01.036

Cited by 5 publications

(2 citation statements)

References 41 publications

(68 reference statements)

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“…Figure 6 also reveals an abundant product ion at m/z 130 corresponding to a neutral loss of 47 Da, which is attributed to extrusion of nitrous acid (HONO). This observation is consistent with the reported gas‐phase fragmentation of other ionised nitroalkanes,3, 14, 21 as well as the solution‐phase thermolysis of vicinal dinitroalkanes 22. The mechanism proposed for the loss of nitrous acid involves the concerted elimination of HONO to form protonated 2,3‐dimethyl‐2‐nitrobut‐3‐ene (Scheme ) and it is supported by the D 12 ‐DMNB spectrum that shows the exclusive loss of HONO (Table 1).…”

Section: Resultssupporting

confidence: 92%

Fragmentation pathways of 2,3‐dimethyl‐2,3‐dinitrobutane cations in the gas phase

Paine

Kirk

Ellis-Steinborner

et al. 2009

Rapid Comm Mass Spectrometry

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Abstract2,3‐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.

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Section: Resultssupporting

confidence: 92%

Fragmentation pathways of 2,3‐dimethyl‐2,3‐dinitrobutane cations in the gas phase

Paine

Kirk

Ellis-Steinborner

et al. 2009

Rapid Comm Mass Spectrometry

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“…Nitrile‐alcohol protonated clusters exhibit also facile water loss thus demonstrating a comparable rearrangement involving isomerization of the most stable approach complex RCN$\cdots$ H+$\cdots$ O(H)R′ to RCN$\cdots$ R′OH

_{2}^{+}

followed by a S N 2 step RCN$\cdots$ R′OH

_{2}^{+}

→ RCNR′' + $\cdots$ OH 2 (Mayer, 1999; Ochran, Annamali, & Mayer, 2000; Ochran & Mayer, 2001). More recently, a similar rearrangement has been proposed to explain the NO 2 H loss from nitroalkane proton bound pairs (Poon & Mayer, 2006). …”

Section: Structural and Energetic Aspects Of The Protonationmentioning

confidence: 76%

Gas‐phase basicities of polyfunctional molecules. Part 1: Theory and methods

Bouchoux

2007

Mass Spectrometry Reviews

116

197

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The experimental and theoretical methods of determination of gas-phase basicities, proton affinities and protonation entropies are presented in a tutorial form. Particularities and limitations of these methods when applied to polyfunctional molecules are emphasized. Structural effects during the protonation process in the gas-phase and their consequences on the corresponding thermochemistry are reviewed and classified. The role of the nature of the basic site (protonation on non-bonded electron pairs or on p-electron systems) and of substituent effects (electrostatic and resonance) are first examined. Then, linear correlations observed between gas-phase basicities and ionization energies or substituent constants are recalled. Hydrogen bonding plays a special part in proton transfer reactions and in the protonation characteristics of polyfunctional molecules. A survey of the main properties of intermolecular and intramolecular hydrogen bonding in both neutral and protonated species is proposed. Consequences on the protonation thermochemistry, particularly of polyfunctional molecules are discussed. Finally, chemical reactions which may potentially occur inside protonated clusters during the measurement of gas-phase basicities or inside a protonated polyfunctional molecule is examined. Examples of bond dissociations with hydride or alkyl migrations, proton transport catalysis, tautomerization, cyclization, ring opening and nucleophilic substitution are presented to illustrate the potentially complex chemistry that may accompany the protonation of polyfunctional molecules. # 2007 Wiley Periodicals, Inc., Mass Spec Rev 26:775-835, 2007

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Current literature in mass spectrometry

2007

J. Mass Spectrom.

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252: 6404-7325. Devoe DL, Lee CS. Microfluidic technologies for MALDI-MS in proteomics. Electrophoresis 2006; 27: 3559. Hjerrild M, Gammeltoft S. Phosphoproteomics toolbox: Computational biology, protein chemistry and mass spectrometry. FEBS Lett 2006; 580: 4764. Kaltashov IA, Zhang MX, Eyles SJ, Abzalimov RR. Investigation of structure, dynamics and function of metalloproteins with electrospray ionization mass spectrometry. Anal Bioanal Chem 2006; 386: 472. Roe MR, Griffin TJ. Gel-free mass spectrometry-based high throughput proteomics: Tools for studying biological response of proteins and proteomes. Proteomics 2006; 6: 4678. Spitzer AR, Chace D. Mass spectrometry in neonatal medicine and clinical diagnostics -The potential use of mass spectrometry in neonatal brain monitoring. Clin Perinatol 2006; 33: 729. Tan DJL, Martinez Arias A. High-throughput localization of organelle proteins by mass spectrometry: A quantum leap for cell biology.

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Competing rearrangement reactions in small gas-phase ionic complexes: The internal SN2 and nitro-nitrite rearrangements in nitroalkane proton-bound pairs

Cited by 5 publications

References 41 publications

Fragmentation pathways of 2,3‐dimethyl‐2,3‐dinitrobutane cations in the gas phase

Fragmentation pathways of 2,3‐dimethyl‐2,3‐dinitrobutane cations in the gas phase

Gas‐phase basicities of polyfunctional molecules. Part 1: Theory and methods

Current literature in mass spectrometry

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