Hydroxyacetylene: Generation and Characterization of the Neutral Molecule, Radical Cation and Dication in the Gas Phase

Baar, Ben van; Weiske, Thomas; Terlouw, Johan K.; Schwarz, Helmut

doi:10.1002/anie.198602821

Cited by 53 publications

(10 citation statements)

References 12 publications

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“…25 Ethynediol has been detected directly by infrared spectroscopy, 26 and its cation has been observed by mass-spectrometry. 27,28 Similar works exist on the singularly substituted ethynol (hydroxyacetylene), 29,30 but HOCCO − and the corresponding neutral radical have not been studied previously. In our experiment, HOCCO − could, in principle, be formed as a product of glyoxalide rearrangement, OHCCO − → HOCCO − , but the analysis shows that this is unlikely to be the case.…”

Section: Introductionmentioning

confidence: 85%

HOCCO versus OCCO: Comparative spectroscopy of the radical and diradical reactive intermediates

Dixon

Xue

Sanov

2016

The Journal of Chemical Physics

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We present a photoelectron imaging study of three glyoxal derivatives: the ethylenedione anion (OCCO(-)), ethynediolide (HOCCO(-)), and glyoxalide (OHCCO(-)). These anions provide access to the corresponding neutral reactive intermediates: the OCCO diradical and the HOCCO and OHCCO radicals. Contrasting the straightforward deprotonation pathway in the reaction of O(-) with glyoxal (OHCCHO), which is expected to yield glyoxalide (OHCCO(-)), OHCCO(-) is shown to be a minor product, with HOCCO(-) being the dominant observed isomer of the m/z = 57 anion. In the HOCCO/OHCCO anion photoelectron spectrum, we identify several electronic states of this radical system and determine the adiabatic electron affinity of HOCCO as 1.763(6) eV. This result is compared to the corresponding 1.936(8) eV value for ethylenedione (OCCO), reported in our recent study of this transient diradical [A. R. Dixon, T. Xue, and A. Sanov, Angew. Chem., Int. Ed. 54, 8764-8767 (2015)]. Based on the comparison of the HOCCO(-)/OHCCO(-) and OCCO(-) photoelectron spectra, we discuss the contrasting effects of the hydrogen connected to the carbon framework or the terminal oxygen in OCCO.

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Section: Introductionmentioning

confidence: 85%

HOCCO versus OCCO: Comparative spectroscopy of the radical and diradical reactive intermediates

Dixon

Xue

Sanov

2016

The Journal of Chemical Physics

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“…Although ynols are believed to exist in interstellar space (25), they were observed on Earth only in the gas phase (26) and in low-temperature matrices (27) before our investigation of them in aqueous solution (28). Primary and secondary ynamines had also been observed only under unusual conditions (29) before our generation of them in aqueous solution (30), probably because they undergo facile rearrangement to ketenimines, Eq.…”

Section: Ynols and Ynaminesmentioning

confidence: 99%

Enols and Other Reactive Species

Chiang

Kresge

1991

Science

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Rapid advances in the chemistry of enols and other reactive species have been made possible recently by the development of methods for generating these short-lived substances in solution under conditions where they can be observed directly and their reactions can be monitored accurately. New laboratory techniques are described and a sample of the new chemistry they have made available is provided; special attention is given to ynols and ynamines and the remarkable effects that the carbon-carbon triple bonds of these substances have on their acid-base properties.

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“…The charge exchange process [5] has made it possible to prepare a variety of unstable or reactive molecules [6] from the corresponding readily available cations or anions I7l. Among the elusive neutrals explored in this way are carbenes [8-101 hypervalent radicals [11][12][13][14], diradicals [9,15], and molecules apt to immediate intermolecular destruction (e.g., carbonic acid [16], ethynol [17], or fluoroformic acid [18]). On the other hand, identification of the neutral fragments eliminated during unimolecular dissociation has enabled answers to persisting questions that pertain to the decomposition mechanisms of both small ions (e.g., ionized aniline [19] or methyl acetate [20][21][22]) as well Most NRMS investigations reported so far have involved charge exchange neutralization of cations (eq 1) and employed high energy collisions with stationary targets for the production and post-ionization of the neutralfs), The internal energy of the incipient neutral (M) formed in the neutralization step is mainly determined by the reaction enthalpy AH" of the electron exchange process ARo = IE(N) -RE(M+), where IE(N) is the vertical ionization energy of the gaseous target that is oxidized and RE(M+) is the vertical recombination energy of the precursor ion that is reduced [5].…”

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confidence: 99%

Internal energy distributions of tungsten hexacarbonyl ions after neutralization—Reionization

Beranová

Wesdemiotis

1994

J. Am. Soc. Mass Spectrom.

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The internal energy distributions P(ε) transferred to W(CO) 6 (+·) during the kiloelectronvolt collisions that occur upon neutralization-reionization (NR) have been estimated based on the relative abundances of the W(CO) 0-6 (+·) products present in NR spectra (thermochemical method). The average internal energy of the incipient {W(CO) 6 (+·) }(*) ions arising after near thermoneutral neutralization with trimethylamine followed by reionization with O2 is ∼9 eV for 8-keV precursor ions and is mainly deposited during reionization, For comparison, the mean internal energy of {W(CO) 6 (+·) }(*) after electron ionization (EO or collisionally activated dissociation (CAD) is ∼ 6 eV. Making the neutralization step endothermic slightly increases the overall excitation gained; however, a large increase in endothermicity (> 16 eV) causes only a modest rise of the average internal energy (<2 eV). The P(ε) curve for NR increases exponentially up to ∼ 6 eV and levels off at higher energies.. showing that the probability of imparting large internal energies (6-17 eV) is high. In sharp contrast, the most probable excitation on CAD is ≤6 eV, and the probability of deposition of larger energies declines exponentially. The mean internal energies after CAD and NR decrease steadily when the kinetic energy is lowered. The structure (minima-maxima) observed in the P(ε) distribution for El, which most likely originates from Franck-Condon factors, is not reproduced in the distributions for NR or high energy CAD, despite the fact that all three methods involve electronic excitation. Because of the large internal energies transferred upon NR, NR mass spectrometry could be particularly useful in the differentiation of ionic isomers with high dissociation but low isomerization thresholds.

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Hydroxyacetylene: Generation and Characterization of the Neutral Molecule, Radical Cation and Dication in the Gas Phase

Cited by 53 publications

References 12 publications

HOCCO versus OCCO: Comparative spectroscopy of the radical and diradical reactive intermediates

HOCCO versus OCCO: Comparative spectroscopy of the radical and diradical reactive intermediates

Enols and Other Reactive Species

Internal energy distributions of tungsten hexacarbonyl ions after neutralization—Reionization

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