Unimolecular Metastable Decomposition of Bis(2,2,2-trifluoroethyl) Ether, CF3CH2OCH2CF3, and Ethyl 2,2,2-Trifluoroethyl Ether, CH3CH2OCH2CF3, upon Electron Ionization.

Tajima, Susumu; Sekiguchi, Osamu; Nakajima, Satoshi; Nibbering, Nico M. M.

doi:10.5702/massspec.50.193

Cited by 4 publications

(1 citation statement)

References 24 publications

(4 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Furthermore, their source generated and most abundant m / z 69 ions appeared to consist of both the trifluoromethyl cation and protonated carbon suboxide, the latter being formed by at least three and four different fragmentation routes from the methyl and ethyl esters, respectively (Tajima et al, 2002a). Heavily fluorinated diethyl ethers showed complex fragmentations upon electron ionization (Tajima et al, 2002b) while the metastable [ M methyl] + ions from 1,1,1‐trifluoroisopropyl methyl ether decomposed via the four competitive channels of carbon monoxide, methyl fluoride, difluorocarbene, and methoxyfluorocarbene elimination (Tajima et al, 2003a).…”

Section: Miscellaneousmentioning

confidence: 99%

Four decades of joy in mass spectrometry

Nibbering

2006

Mass Spectrometry Reviews

Self Cite

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

Section: Miscellaneousmentioning

confidence: 99%

Four decades of joy in mass spectrometry

Nibbering

2006

Mass Spectrometry Reviews

Self Cite

View full text Add to dashboard Cite

show abstract

Current literature in mass spectrometry

2003

J. Mass Spectrom.

View full text Add to dashboard Cite

In order to keep subscribers up‐to‐date with the latest developments in their field, John Wiley & Sons are providing a current awareness service in each issue of the journal. The bibliography contains newly published material in the field of mass spectrometry. Each bibliography is divided into 11 sections: 1 Books, Reviews & Symposia; 2 Instrumental Techniques & Methods; 3 Gas Phase Ion Chemistry; 4 Biology/Biochemistry: Amino Acids, Peptides & Proteins; Carbohydrates; Lipids; Nucleic Acids; 5 Pharmacology/Toxicology; 6 Natural Products; 7 Analysis of Organic Compounds; 8 Analysis of Inorganics/Organometallics; 9 Surface Analysis; 10 Environmental Analysis; 11 Elemental Analysis. Within each section, articles are listed in alphabetical order with respect to author (4 Weeks journals ‐ Search completed at 4th. June. 2003)

show abstract

Unimolecular Gas-Phase Reactions of Ionized Organo-Silicon Compounds. Part XVI. (CH3)3SiOCH2CH3 and (CH3)3SiOCH2CF3

Tajima

Hiroi

Nakajima

et al. 2003

J. Mass Spectrom. Soc. Jpn.

Self Cite

View full text Add to dashboard Cite

The unimolecular metastable decompositions of ethoxytrimethylsilane ((CH3)3SiOCH2CH3; 1, MW: 118) and its fluorine analogue, 2,2,2-trifluoroethoxytrimethylsilane ((CH3)3SiOCH2CF3, 2; MW: 172) induced by electron ionization, have been investigated by use of mass-analyzed ion kinetic energy (MIKE) spectrometry and D-labeling. Both molecular ions are formed in low abundance. The fragmentation of 1 ῌῌ is di#erent from that of 2 ῌῌ , except for the loss of CH3 from the corresponding molecular ions. The MIKE spectra of the [M῍CH3]ῌ ions from 1 ῌῌ and 2 ῌῌ gave five and three fragment ions, respectively. Two of the five reactions for 1 leading to the formation of the ion at m/z 101, (CH3)2Siῌ OCH῎CH2, and m/z 61, CH3Si ῌ HOH, concern new mechanistic pathways, which were not described in previous reports. Skeletal rearrangement by among others F and CF3 migrations, occurs during the fragmentation of the [M῍CH3] ῌ ions from 2 ῌῌ . The m/z 61 ions from 2 ῌῌ are both CH2OCF ῌ (or CH2FCO ῌ etc.) and CH3Si ῌ HOH.

show abstract

Unimolecular Metastable Decomposition of Bis(2,2,2-trifluoroethyl) Ether, CF3CH2OCH2CF3, and Ethyl 2,2,2-Trifluoroethyl Ether, CH3CH2OCH2CF3, upon Electron Ionization.

Cited by 4 publications

References 24 publications

Four decades of joy in mass spectrometry

Four decades of joy in mass spectrometry

Current literature in mass spectrometry

Unimolecular Gas-Phase Reactions of Ionized Organo-Silicon Compounds. Part XVI. (CH3)3SiOCH2CH3 and (CH3)3SiOCH2CF3

Contact Info

Product

Resources

About