Experimental Studies of Allene, Methylacetylene, and the Propargyl Radical: Bond Dissociation Energies, Gas-Phase Acidities, and Ion–Molecule Chemistry

Marin S. Robinson, Veronica M. Bierbaum, Charles H. DePuy, Mark L. Polak, W. C. Lineberger

Research output: Contribution to journalArticle

144 Scopus citations

Abstract

Electron affinities and ΔHacid are combined in a thermochemical cycle to arrive at bond dissociation energies for allene, methylacetylene, and the propargyl radical: D0(CH2=C=CH—H) = 88.7 ± 3 kcal mol–1, D0(H–CH2C≡CH) = 90.3 ± 3 kcal mol–1, D0(CH3C≡C–H) = 130.2 ± 3 kcal mol–1, and D0(CH2=C=Ċ–H) = 100 ± 5 kcal mol–1. Electron affinity measurements were determined using negative ion photoelectron spectroscopy and yielded the following for the propargyl, 1-propynyl, and propadienylidene radicals: EA(CH2=C=ĊH) = 0.918 ± 0.008 eV, EA(CH3C≡Ċ) = 2.718 ± 0.008 eV, and EA(CH2=C=Ċ) = 1.794 ± 0.008 eV. Gas-phase acidity measurements were made using proton transfer kinetics in a flowing afterglow/selected-ion flow tube and yielded the following for allene, methylacetylene, and the propargyl radical: ΔGacid(CH2=C=CH–H) = 372.8 ± 3 kcal mol–1, ΔGacid(H–CH2C≡ĊH) = 374.7 ± 3 kcal mol–1, ΔGacid(CH3C≡C–H) = 373.4 ± 2 kcal mol–1, and ΔGacid(CH2=C=ĊH) = 364 ± 5 kcal mol–1. AGacid was converted to ΔHacid by employing ΔSacid: ΔHacid(CH2=C=CH–H) = 381.1 ± 3 kcal mol–1, ΔHacid(H-CH2C≡CH) = 382.7 ± 3 kcal mol–1, ΔHacid(CH3C=C–H) = 381.1 ± 3 kcal mol–1, and ΔHacid(CH2=C=ĊH) = 372 ± 5 kcal mol–1. Evidence is provided for the isomerization of the allenyl anion (CH2=C=CH) to the 1-propynyl anion (CH3C≡C) in the proton transfer reactions of CH2=C=CH with CH3OH and CH3CH2OH. This complexity limits the precision of experimental measurements. This study explores the intricacies of determining gas phase acidity values by proton transfer reactions for systems in which isomerization can occur.

Original languageEnglish (US)
Pages (from-to)6766-6778
Number of pages13
JournalJournal of the American Chemical Society
Volume117
Issue number25
DOIs
StatePublished - Jan 1 1995
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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