Reactions of 2-propanol with Cu+ in the gas phase: A density functional theory study

Mu Jeng Cheng, Ching-Han Hu, Chen Sheng Yeh

Research output: Contribution to journalArticle

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Abstract

The gas phase reactions between Cu+ and 2-propanol have been investigated using density functional theory at the B3LYP/6-311++G(d) and B3LYP/6-311++G(d,p) levels of theories. Seven reaction pathways have been studied. Of all reaction paths, the mechanism involving an electrophile-induced one step syn elimination of H2O has the lowest energy barrier. Dehydration also occurs via the intermediate corresponding to C-O insertion of Cu+. On the H2 elimination channel, reaction begins with C-H insertion of Cu+, followed by hydrogen migrations to form H2-Cu+-acetone or the H2-Cu+-2-propenol intermediates. Our results show that the reaction with copper cation insertion into the H-OCH(CH3)2 bond is unlikely, for its activation energy is 24.5 kcal/mol higher than those of the reactants (Cu+ and 2-propanol). The mechanism involving C-C insertion of Cu+ is also energetically unfavorable. The predicted potential energy surface of reaction and relative energies of the fragmentation products are consistent with available gas phase experiments.

Original languageEnglish
Pages (from-to)11570-11580
Number of pages11
JournalJournal of Physical Chemistry A
Volume106
Issue number47
DOIs
Publication statusPublished - 2002 Nov 28

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2-Propanol
Density functional theory
Gases
vapor phases
density functional theory
Potential energy surfaces
insertion
Energy barriers
Acetone
Dehydration
Cations
Copper
Hydrogen
Activation energy
elimination
Experiments
dehydration
acetone
fragmentation
potential energy

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

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abstract = "The gas phase reactions between Cu+ and 2-propanol have been investigated using density functional theory at the B3LYP/6-311++G(d) and B3LYP/6-311++G(d,p) levels of theories. Seven reaction pathways have been studied. Of all reaction paths, the mechanism involving an electrophile-induced one step syn elimination of H2O has the lowest energy barrier. Dehydration also occurs via the intermediate corresponding to C-O insertion of Cu+. On the H2 elimination channel, reaction begins with C-H insertion of Cu+, followed by hydrogen migrations to form H2-Cu+-acetone or the H2-Cu+-2-propenol intermediates. Our results show that the reaction with copper cation insertion into the H-OCH(CH3)2 bond is unlikely, for its activation energy is 24.5 kcal/mol higher than those of the reactants (Cu+ and 2-propanol). The mechanism involving C-C insertion of Cu+ is also energetically unfavorable. The predicted potential energy surface of reaction and relative energies of the fragmentation products are consistent with available gas phase experiments.",
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Reactions of 2-propanol with Cu+ in the gas phase : A density functional theory study. / Cheng, Mu Jeng; Hu, Ching-Han; Yeh, Chen Sheng.

In: Journal of Physical Chemistry A, Vol. 106, No. 47, 28.11.2002, p. 11570-11580.

Research output: Contribution to journalArticle

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