Studies of the gas phase reactions of protonated methanol with methanol using oxygen-18 and deuterium labeling

Dang, Thuy Thanh; Bierbaum, Veronica M.

doi:10.1016/0168-1176(92)80086-g

Cited by 17 publications

(14 citation statements)

References 19 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…4b. The rearrangement barrier (TS (8)(9)(10)(11)(12)(13)(14)(15)(16), TS2) is decreased substantially compared to that of the other nitroalkane proton-bound pairs, in good agreement with the experimental result. However, the barrier is lowered to an extent that the rearrangement process evolves over a rather flat surface, with the alkyl cation transfer barrier TS2 lying close in energy to the barrier (TS1) for forming the intermediate (8,INT) from the original proton-bound dimer 4.…”

Section: Nitrous Acid Loss Channelsupporting

confidence: 87%

“…Proton-bound pairs of alcohols (ROH)(R OH)H + exhibit an almost universal tendency to lose H 2 O [1][2][3][4][5]. Calculations [6][7][8][9][10][11] and experiments [12][13][14][15][16] on the methanol proton-bound dimer indicated that isomerization proceeds via an internal S N 2-type reaction. Work from our laboratory and that of other labs also showed that the family of methyl-substituted nitrile-alcohol proton-bound pairs [9,11,[17][18][19][20] and dimethyl ether protonbound dimer [21] loses water and methanol in a similar fashion.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

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

Poon

Mayer

2006

International Journal of Mass Spectrometry

View full text Add to dashboard Cite

Section: Nitrous Acid Loss Channelsupporting

confidence: 87%

Section: Introductionmentioning

confidence: 99%

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

Poon

Mayer

2006

International Journal of Mass Spectrometry

View full text Add to dashboard Cite

“…Then let the reaction go and eject continuously CH

_{3}^{16}

_{2}^{+}

, formed during the reaction by the facile proton transfer from CH

_{3}^{18}

_{2}^{+}

to CH

_{3}^{16}

OH, from the FTICR cell with the result that protonated dimethyl ether containing the 16 O label was indeed the major (∼75%) product ion under the applied experimental conditions (Kleingeld & Nibbering, 1982a). This result has led to a lively debate and a number of both experimental and theoretical studies afterwards that have confirmed the S N 2 mechanism, but also have uncovered details of the competing proton transfer channel (Dang & Bierbaum, 1992; Bouchoux & Choret, 1997). Another early project, that was undertaken because of a previous hydride ion transfer study between methoxide and formaldehyde (Ingemann, Kleingeld, & Nibbering, 1982), concerns the reaction of the hydroxide ion with formaldehyde that led to the observation of a peak at m / z 19 in the FTICR spectrum.…”

Section: The Years Of Fourier Transform Ion Cyclotron Resonance mentioning

confidence: 99%

Four decades of joy in mass spectrometry

Nibbering

2006

Mass Spectrometry Reviews

View full text Add to dashboard Cite

Tremendous developments in mass spectrometry have taken place in the last 40 years. This holds for both the science and the instrumental revolutions in this field. In chemistry the research was heavily focused on organic molecules that upon electron ionization fragmented via complex mechanistic pathways as shown by isotopic labeling experiments. These studies, including ion structure determinations, were performed with use of double focusing mass spectrometers of both conventional and reversed geometry, and equipped with various types of metastable ion scanning and collision-induced dissociation techniques developed by physical and analytical chemists. Time-resolved mass spectrometry by use of the field ionization kinetics method, developed by physical chemists, was another powerful way to unravel details of unimolecular gas phase ion dissociations. Then the development of new ionization methods, such as desorption chemical ionization, field desorption, and fast atom bombardment permitted not only to analyze unvolatile, thermally labile and higher molecular weight compounds, but also to study their chemical behavior in the gas phase, initially with use of double focusing instruments and later on with multisector and hybrid mass spectrometers. These ionization methods also enabled to study organometallic compounds and increasingly the field of medium-sized to large biomolecules, the latter being exploded in the last decade by the development of electrospray- and matrix-assisted laser desorption ionization/time-of-flight mass spectrometry. Another area of research concerned the bimolecular chemistry of organic ions with organic molecules in the gas phase. Initially this was performed with use of among others drift-cell ion cyclotron resonance spectroscopy, that later on was replaced by the developed method of ion trapping and Fourier transform ion cyclotron resonance. Combination of the latter with the afore-mentioned ionization methods has shifted also in this case the research on organic molecules to organometallic/inorganic systems, and predominantly to biomolecules in the last decade. This invited review will describe the research efforts made by the author's group over the last 40 years together with some personal experiences during his career.

show abstract

“…There are numerous experimental investigations by means of various experimental techniques exploring different pressure (from 1-10 −4 mbar in ion flow tube experiments to 10 −6 -10 −7 mbar in ion cyclotron resonance experiments) and temperature (from 293 K to 670 K) ranges (Karpas & Meot-Ner 1989;Morris et al 1991;Dang & Bierbaum 1992;Fridgen et al 2001). The results are in partial disagreement, especially on the product branching ratio.…”

mentioning

confidence: 99%

Interstellar dimethyl ether gas-phase formation: a quantum chemistry and kinetics study

Skouteris

Balucani

Ceccarelli

et al. 2018

Monthly Notices of the Royal Astronomical Society

View full text Add to dashboard Cite

Dimethyl ether is one of the most abundant interstellar complex organic molecules. Yet its formation route remains elusive. In this work, we have performed electronic structure and kinetics calculations to derive the rate coefficients for two ion-molecule reactions recently proposed as a gas-phase formation route of dimethyl ether in interstellar objects, namelyA comparison with previous experimental rate coefficients for the reaction CH 3 OH + CH 3 OH + 2 sustains the accuracy of the present calculations and allow a more reliable extrapolation at the low temperatures of interest in interstellar objects (10-100 K). The rate coefficient for the reaction (CH 3 ) 2 OH + + NH 3 is, instead, provided for the first time ever. The rate coefficients derived in this work essentially confirm the prediction by Taquet et al. (2016) concerning dimethyl ether formation in hot cores/corinos. Nevertheless, this formation route cannot be efficient in cold objects (like prestellar cores) where dimethyl ether is also detected, because ammonia has a very low abundance in those environments.

show abstract

Studies of the gas phase reactions of protonated methanol with methanol using oxygen-18 and deuterium labeling

Cited by 17 publications

References 19 publications

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

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

Four decades of joy in mass spectrometry

Interstellar dimethyl ether gas-phase formation: a quantum chemistry and kinetics study

Contact Info

Product

Resources

About