Intracluster ion-molecule reactions of Ti+ with C 2H5OH and CF3CH2OH clusters

Influence of fluorine substituents on chemical reactivity

Young Mi Koo, Tae Kyu Kim, Dong Woon Jung, Kwang Woo Jung

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

A laser ablation-molecular beam/reflectron time-of-flight mass spectrometric technique was used to investigate the ion-molecule reactions that proceed within Ti+(ROH)n (R = C2H5, CF3CH2) heterocluster ions. The mass spectra exhibit a major sequence of cluster ions with the formula Ti+(OR) m(ROH)n (m = 1, 2), which is attributed to sequential insertions of Ti+ into the O-H bond of C2H5OH or CF3CH2OH molecules within the heteroclusters, followed by H eliminations. The TiO+ and TiOH+ ions produced from the reactions of Ti+ with C2H5OH are interpreted as arising from insertion of Ti+ into the C-O bond, followed by C2H5 and C2H6 eliminations, respectively. When Ti+ reacted with CF 3CH2OH, by contrast, considerable contributions from TiFOH+, TiF2+, and TiF2OH + ions were observed in the mass spectrum of the reaction products, indicating that F and OH abstractions are the dominant product channels. Ab initio calculations of the complex of Ti+ with 2,2,2-trifluoroethanol show that the minimum energy structure is that in which Ti+ is attached to the O atom and one of the three F atoms of 2,2,2-trifluoroethanol, forming a five-membered ring. Isotope-labeling experiments additionally show that the chemical reactivity of heterocluster ions is greatly influenced by the presence of fluorine substituents and cluster size. The reaction energetics and formation mechanisms of the observed heterocluster ions are discussed.

Original languageEnglish
Pages (from-to)13724-13730
Number of pages7
JournalJournal of Physical Chemistry A
Volume110
Issue number51
DOIs
Publication statusPublished - 2006 Dec 28

Fingerprint

Chemical reactivity
Fluorine
fluorine
reactivity
Ions
Molecules
molecules
ions
Trifluoroethanol
mass spectra
insertion
elimination
Atoms
Molecular beams
Laser ablation
Reaction products
Isotopes
reaction products
Labeling
molecular beams

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

@article{9dec06a9c3b049af8af286a7a993216b,
title = "Intracluster ion-molecule reactions of Ti+ with C 2H5OH and CF3CH2OH clusters: Influence of fluorine substituents on chemical reactivity",
abstract = "A laser ablation-molecular beam/reflectron time-of-flight mass spectrometric technique was used to investigate the ion-molecule reactions that proceed within Ti+(ROH)n (R = C2H5, CF3CH2) heterocluster ions. The mass spectra exhibit a major sequence of cluster ions with the formula Ti+(OR) m(ROH)n (m = 1, 2), which is attributed to sequential insertions of Ti+ into the O-H bond of C2H5OH or CF3CH2OH molecules within the heteroclusters, followed by H eliminations. The TiO+ and TiOH+ ions produced from the reactions of Ti+ with C2H5OH are interpreted as arising from insertion of Ti+ into the C-O bond, followed by C2H5 and C2H6 eliminations, respectively. When Ti+ reacted with CF 3CH2OH, by contrast, considerable contributions from TiFOH+, TiF2+, and TiF2OH + ions were observed in the mass spectrum of the reaction products, indicating that F and OH abstractions are the dominant product channels. Ab initio calculations of the complex of Ti+ with 2,2,2-trifluoroethanol show that the minimum energy structure is that in which Ti+ is attached to the O atom and one of the three F atoms of 2,2,2-trifluoroethanol, forming a five-membered ring. Isotope-labeling experiments additionally show that the chemical reactivity of heterocluster ions is greatly influenced by the presence of fluorine substituents and cluster size. The reaction energetics and formation mechanisms of the observed heterocluster ions are discussed.",
author = "Koo, {Young Mi} and Kim, {Tae Kyu} and Jung, {Dong Woon} and Jung, {Kwang Woo}",
year = "2006",
month = "12",
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doi = "10.1021/jp064596+",
language = "English",
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Intracluster ion-molecule reactions of Ti+ with C 2H5OH and CF3CH2OH clusters : Influence of fluorine substituents on chemical reactivity. / Koo, Young Mi; Kim, Tae Kyu; Jung, Dong Woon; Jung, Kwang Woo.

In: Journal of Physical Chemistry A, Vol. 110, No. 51, 28.12.2006, p. 13724-13730.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Intracluster ion-molecule reactions of Ti+ with C 2H5OH and CF3CH2OH clusters

T2 - Influence of fluorine substituents on chemical reactivity

AU - Koo, Young Mi

AU - Kim, Tae Kyu

AU - Jung, Dong Woon

AU - Jung, Kwang Woo

PY - 2006/12/28

Y1 - 2006/12/28

N2 - A laser ablation-molecular beam/reflectron time-of-flight mass spectrometric technique was used to investigate the ion-molecule reactions that proceed within Ti+(ROH)n (R = C2H5, CF3CH2) heterocluster ions. The mass spectra exhibit a major sequence of cluster ions with the formula Ti+(OR) m(ROH)n (m = 1, 2), which is attributed to sequential insertions of Ti+ into the O-H bond of C2H5OH or CF3CH2OH molecules within the heteroclusters, followed by H eliminations. The TiO+ and TiOH+ ions produced from the reactions of Ti+ with C2H5OH are interpreted as arising from insertion of Ti+ into the C-O bond, followed by C2H5 and C2H6 eliminations, respectively. When Ti+ reacted with CF 3CH2OH, by contrast, considerable contributions from TiFOH+, TiF2+, and TiF2OH + ions were observed in the mass spectrum of the reaction products, indicating that F and OH abstractions are the dominant product channels. Ab initio calculations of the complex of Ti+ with 2,2,2-trifluoroethanol show that the minimum energy structure is that in which Ti+ is attached to the O atom and one of the three F atoms of 2,2,2-trifluoroethanol, forming a five-membered ring. Isotope-labeling experiments additionally show that the chemical reactivity of heterocluster ions is greatly influenced by the presence of fluorine substituents and cluster size. The reaction energetics and formation mechanisms of the observed heterocluster ions are discussed.

AB - A laser ablation-molecular beam/reflectron time-of-flight mass spectrometric technique was used to investigate the ion-molecule reactions that proceed within Ti+(ROH)n (R = C2H5, CF3CH2) heterocluster ions. The mass spectra exhibit a major sequence of cluster ions with the formula Ti+(OR) m(ROH)n (m = 1, 2), which is attributed to sequential insertions of Ti+ into the O-H bond of C2H5OH or CF3CH2OH molecules within the heteroclusters, followed by H eliminations. The TiO+ and TiOH+ ions produced from the reactions of Ti+ with C2H5OH are interpreted as arising from insertion of Ti+ into the C-O bond, followed by C2H5 and C2H6 eliminations, respectively. When Ti+ reacted with CF 3CH2OH, by contrast, considerable contributions from TiFOH+, TiF2+, and TiF2OH + ions were observed in the mass spectrum of the reaction products, indicating that F and OH abstractions are the dominant product channels. Ab initio calculations of the complex of Ti+ with 2,2,2-trifluoroethanol show that the minimum energy structure is that in which Ti+ is attached to the O atom and one of the three F atoms of 2,2,2-trifluoroethanol, forming a five-membered ring. Isotope-labeling experiments additionally show that the chemical reactivity of heterocluster ions is greatly influenced by the presence of fluorine substituents and cluster size. The reaction energetics and formation mechanisms of the observed heterocluster ions are discussed.

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