Metastable ion characteristics. XXXIII. Long-lived .beta.-phenylethyl and ethylenebenzenium cations in the gas phase

Nibbering, Nico M. M.; Nishishita, Takao; Sande, C. C. Van De; McLafferty, Fred W.

doi:10.1021/ja00824a108

Cited by 29 publications

(11 citation statements)

References 2 publications

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“…Isopropyl Dihydrocinnamate. EI-MS: m/z (%), 192 [M +• , 20], 150 (43), 133 (26), 105 (58), 104 (100), 103 (17), 91 (74), 79 (16), 78 (18), 77 (28), 65 (11), 51 (15), 43 (30).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Ambulation of Incipient Proton during Gas-Phase Dissociation of Protonated Alkyl Dihydrocinnamates

Zhang

Errabelli

et al. 2015

J. Org. Chem.

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Upon activation in the gas phase, protonated alkyl dihydrocinnamates undergo an alcohol loss. However, the mechanism followed is not a simple removal of an alkanol molecule after a protonation on the alkoxy group. The mass spectrum of the m/z 166 ion for deuteron-charged methyl dihydrocinnamate showed two peaks of 1:5 intensity ratio at m/z 133 and 134 to confirm that the incipient proton is mobile. The proton initially attached to the carbonyl group migrates to the ring and randomizes before a subsequent transfer of one of the ring protons to the alkoxy group for the concomitant alcohol elimination. Moreover, protonated methyl dihydrocinnamate undergoes more than one H/D exchange. The spectra recorded from m/z 167 and 168 ions obtained for di- and tri-deuterio isotopologues showed peak pairs at m/z 134, 135 and 135, 136, at 1:2 and 1:1 intensity ratios, respectively, confirming the benzenium ion intermediate achieves complete randomization before the proton transfer. Additionally, protonated higher esters of alkyl dihydrocinnamates undergo a cleavage of the O-CH2 bond to form an ion/neutral complex, which, upon activation, dissociates generating a carbenium ion and dihydrocinnamic acid, or rearranges to generate protonated dihydrocinnamic acid and an alkene by a nonspecific proton transfer.

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“…Isopropyl Dihydrocinnamate. EI-MS: m/z (%), 192 [M +• , 20], 150 (43), 133 (26), 105 (58), 104 (100), 103 (17), 91 (74), 79 (16), 78 (18), 77 (28), 65 (11), 51 (15), 43 (30).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Ambulation of Incipient Proton during Gas-Phase Dissociation of Protonated Alkyl Dihydrocinnamates

Zhang

Errabelli

et al. 2015

J. Org. Chem.

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“…The CA peaks of abundance most sensitive to isomeric structure are those at m/e 51,89, 90, and 91, while the m/e 39 peak abundance is nearly independent (±1.5%) of isomeric identity. Major CA peaks occur at the following masses (approximate abundances in parentheses): 27 (5), 39 (10), 41 (1), 51 (15)(16)(17)(18)(19)(20)(21)(22)(23)(24)(25)(26)(27)(28)(29)(30), 53 (5), 63 (11), 65 (8). 74 (4), 75 (5), 101 (2), 102 (10-25), and 89, 90, and 91 (11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21)(22).…”

Section: Methodsmentioning

confidence: 99%

“…Major CA peaks occur at the following masses (approximate abundances in parentheses): 27 (5), 39 (10), 41 (1), 51 (15)(16)(17)(18)(19)(20)(21)(22)(23)(24)(25)(26)(27)(28)(29)(30), 53 (5), 63 (11), 65 (8). 74 (4), 75 (5), 101 (2), 102 (10-25), and 89, 90, and 91 (11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21)(22). The abundance of m/e 88 is <1% of the sum of those of m/e 89, 90, and 91.…”

Section: Methodsmentioning

confidence: 99%

“…Methyltropylium Ion (4). In contrast to the other molecular ions studied, those of methylcycloheptatrigne (15), xylene (16), and ethylbenzene (17) yield CgH9+ metastable ions which decompose by loss of CH3 to give m/e 90. This fragmentation is consistent with the methyltropylium structure (4) for the decomposing CgH9+ ions (at least CH3 loss seems less likely for 1-3 and 5-14), and the formation of 4 is analogous to the predominant formation of tropylium ions from cycloheptatriene and toluene ions.…”

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confidence: 86%

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Collisional activation and metastable ion characteristics. 53. Thirteen stable isomers of gaseous C8H9+ cations

Koeppel¹,

Sande²,

Nibbering³

et al. 1977

J. Am. Chem. Soc.

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“…Together with Dr. Takao Nishishita from Japan and Dr. Chris van de Sande from Belgium (we were called the three musketeers) three publications eventually appeared, two on C 8 H

_{9}^{+}

ions (Nibbering et al . , 1974a; Köppel et al . , 1977), and one on the C 9 H 11 O + ion from 2‐methyl‐2‐phenylpropane‐1,3‐diol (Nibbering et al .…”

Section: The Years Of Double Focusing Sector Mass Spectrometry Untmentioning

confidence: 99%

Four decades of joy in mass spectrometry

Nibbering

2006

Mass Spectrometry Reviews

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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.

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Metastable ion characteristics. XXXIII. Long-lived .beta.-phenylethyl and ethylenebenzenium cations in the gas phase

Cited by 29 publications

References 2 publications

Ambulation of Incipient Proton during Gas-Phase Dissociation of Protonated Alkyl Dihydrocinnamates

Ambulation of Incipient Proton during Gas-Phase Dissociation of Protonated Alkyl Dihydrocinnamates

Collisional activation and metastable ion characteristics. 53. Thirteen stable isomers of gaseous C8H9+ cations

Four decades of joy in mass spectrometry

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