Intracluster cyclization reaction producing a benzene derivative: Photoionization mass spectrometric study of alkali metal-methyl propiolate clusters

Hironori Tsunoyama, Keijiro Ohshimo, Fuminori Misaizu, Koichi Ohno

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Size-dependent stability and intracluster reactions have been investigated by photoionization mass spectrometry for alkali metal (M; Li, Na, and K)-methyl propiolate (MP; HC≡CCOOCH3) molecules clusters. In the photoionization mass spectra, the intensities of M+(MP)3 ions (M=Na and K) were unexpectedly high, whereas no intensity anomaly was observed in Li+(MP)n mass spectrum. The intensity anomaly can be explained by intracluster cyclization reaction induced by electron transfer from the metal atom and resulting a stable benzene derivative formation. Ion intensities of M+(MP)n(H2O) relative to M+(MP)n have a minimum at n=3 in Na and K systems. This result is owing to evaporation of water and/or MP molecules following exothermic cyclization reaction. Fragment ions with a loss of CH 2 were also observed predominantly from M(MP)2 in all metal systems. These ions are expected to be produced by hydrolysis in M(MP)n(H2O) clusters producing a HC≡CCOOH molecule. The difference between lithium and other alkali metals is due to the rigidity of clusters with respect to deformation into geometry leading to the polymerization reaction.

Original languageEnglish
Pages (from-to)41-50
Number of pages10
JournalInternational Journal of Mass Spectrometry
Volume232
Issue number1
DOIs
Publication statusPublished - 2004 Mar 1
Externally publishedYes

Fingerprint

Benzene Derivatives
Alkali Metals
Photoionization
Cyclization
Alkali metals
alkali metals
photoionization
Benzene
benzene
Ions
Derivatives
mass spectra
Molecules
ions
Metals
anomalies
molecules
exothermic reactions
Lithium
rigidity

Keywords

  • Alkali metal
  • Cyclization
  • Intracluster reaction
  • Photoionization
  • Polymerization

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy

Cite this

Intracluster cyclization reaction producing a benzene derivative : Photoionization mass spectrometric study of alkali metal-methyl propiolate clusters. / Tsunoyama, Hironori; Ohshimo, Keijiro; Misaizu, Fuminori; Ohno, Koichi.

In: International Journal of Mass Spectrometry, Vol. 232, No. 1, 01.03.2004, p. 41-50.

Research output: Contribution to journalArticle

@article{fe60ecb9135d4038ad5b2513f196a5ba,
title = "Intracluster cyclization reaction producing a benzene derivative: Photoionization mass spectrometric study of alkali metal-methyl propiolate clusters",
abstract = "Size-dependent stability and intracluster reactions have been investigated by photoionization mass spectrometry for alkali metal (M; Li, Na, and K)-methyl propiolate (MP; HC≡CCOOCH3) molecules clusters. In the photoionization mass spectra, the intensities of M+(MP)3 ions (M=Na and K) were unexpectedly high, whereas no intensity anomaly was observed in Li+(MP)n mass spectrum. The intensity anomaly can be explained by intracluster cyclization reaction induced by electron transfer from the metal atom and resulting a stable benzene derivative formation. Ion intensities of M+(MP)n(H2O) relative to M+(MP)n have a minimum at n=3 in Na and K systems. This result is owing to evaporation of water and/or MP molecules following exothermic cyclization reaction. Fragment ions with a loss of CH 2 were also observed predominantly from M(MP)2 in all metal systems. These ions are expected to be produced by hydrolysis in M(MP)n(H2O) clusters producing a HC≡CCOOH molecule. The difference between lithium and other alkali metals is due to the rigidity of clusters with respect to deformation into geometry leading to the polymerization reaction.",
keywords = "Alkali metal, Cyclization, Intracluster reaction, Photoionization, Polymerization",
author = "Hironori Tsunoyama and Keijiro Ohshimo and Fuminori Misaizu and Koichi Ohno",
year = "2004",
month = "3",
day = "1",
doi = "10.1016/j.ijms.2003.11.003",
language = "English",
volume = "232",
pages = "41--50",
journal = "International Journal of Mass Spectrometry",
issn = "1387-3806",
publisher = "Elsevier",
number = "1",

}

TY - JOUR

T1 - Intracluster cyclization reaction producing a benzene derivative

T2 - Photoionization mass spectrometric study of alkali metal-methyl propiolate clusters

AU - Tsunoyama, Hironori

AU - Ohshimo, Keijiro

AU - Misaizu, Fuminori

AU - Ohno, Koichi

PY - 2004/3/1

Y1 - 2004/3/1

N2 - Size-dependent stability and intracluster reactions have been investigated by photoionization mass spectrometry for alkali metal (M; Li, Na, and K)-methyl propiolate (MP; HC≡CCOOCH3) molecules clusters. In the photoionization mass spectra, the intensities of M+(MP)3 ions (M=Na and K) were unexpectedly high, whereas no intensity anomaly was observed in Li+(MP)n mass spectrum. The intensity anomaly can be explained by intracluster cyclization reaction induced by electron transfer from the metal atom and resulting a stable benzene derivative formation. Ion intensities of M+(MP)n(H2O) relative to M+(MP)n have a minimum at n=3 in Na and K systems. This result is owing to evaporation of water and/or MP molecules following exothermic cyclization reaction. Fragment ions with a loss of CH 2 were also observed predominantly from M(MP)2 in all metal systems. These ions are expected to be produced by hydrolysis in M(MP)n(H2O) clusters producing a HC≡CCOOH molecule. The difference between lithium and other alkali metals is due to the rigidity of clusters with respect to deformation into geometry leading to the polymerization reaction.

AB - Size-dependent stability and intracluster reactions have been investigated by photoionization mass spectrometry for alkali metal (M; Li, Na, and K)-methyl propiolate (MP; HC≡CCOOCH3) molecules clusters. In the photoionization mass spectra, the intensities of M+(MP)3 ions (M=Na and K) were unexpectedly high, whereas no intensity anomaly was observed in Li+(MP)n mass spectrum. The intensity anomaly can be explained by intracluster cyclization reaction induced by electron transfer from the metal atom and resulting a stable benzene derivative formation. Ion intensities of M+(MP)n(H2O) relative to M+(MP)n have a minimum at n=3 in Na and K systems. This result is owing to evaporation of water and/or MP molecules following exothermic cyclization reaction. Fragment ions with a loss of CH 2 were also observed predominantly from M(MP)2 in all metal systems. These ions are expected to be produced by hydrolysis in M(MP)n(H2O) clusters producing a HC≡CCOOH molecule. The difference between lithium and other alkali metals is due to the rigidity of clusters with respect to deformation into geometry leading to the polymerization reaction.

KW - Alkali metal

KW - Cyclization

KW - Intracluster reaction

KW - Photoionization

KW - Polymerization

UR - http://www.scopus.com/inward/record.url?scp=1542381020&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=1542381020&partnerID=8YFLogxK

U2 - 10.1016/j.ijms.2003.11.003

DO - 10.1016/j.ijms.2003.11.003

M3 - Article

AN - SCOPUS:1542381020

VL - 232

SP - 41

EP - 50

JO - International Journal of Mass Spectrometry

JF - International Journal of Mass Spectrometry

SN - 1387-3806

IS - 1

ER -