Thermochemistry of Simple Enols and Enol Cation Radicals Revisited. A G2(MP2) ab Initio Study

František Tureček, Chris Cramer

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79 Scopus citations

Abstract

Simple enols, vinyl alcohol (1), propen-2-ol (2), (E)-propen-l-ol (3), (Z)-propen-1-ol (4), (E)-2-buten-2-ol (5), and (Z)-2-buten-2-ol (6), and their cation radicals are investigated by ab initio calculations at the Gaussian 2 (MP2) level of theory. Syn-planar conformations are found to be thermodynamically more stable for gaseous 1, 2, 3, 5, and 6, which give ΔG°298(anti-syn) = 2.5, 4.0, 1.4, 5.6, and 3.3 kJ mol-1, respectively. The syn form of 4 is thermochemically favored by ΔH°298(anti-syn) = 1.2 kJ mol-1, but disfavored by entropy, which leads to ΔG°298-(anti-syn) = -0.5 kJ mol-1. The enols are predicted to exist as mixtures of rotamers in the gas phase. Standard enthalpies of formation for 1, 2, 3, 4, 5, and 6 are calculated from isodesmic reactions as -123, -167, -147, -148, -190, and -195 kJ mol-1, respectively. Enol cation radicals uniformly prefer anti conformations with ΔG°298-(syn-anti) = 3.5-8.1 kJ mol-1. Standard enthalpies of formation from isodesmic and isogyric reactions were calculated as 765, 677, 682, 682, 603, and 601 kJ mol-1 for 1•+, 2•+, 3•+, 4•+, 5•+, and 6•+, respectively. The calculated ΔH°f,298 show good agreement with experimental estimates for 1 and 1•+, but diverge for the higher enols. The divergence is significantly diminished when 298 K enthalpy corrections are included in the experimental threshold energies. The calculated adiabatic ionization energies are in excellent to fair agreement with experimental data for 1, 2, 3, and 4, but show 0.2—0.3 eV deviations for 5 and 6.

Original languageEnglish (US)
Pages (from-to)12243-12253
Number of pages11
JournalJournal of the American Chemical Society
Volume117
Issue number49
DOIs
StatePublished - Jan 1 1995

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