Gas-Phase Infrared and NMR Investigation of the Conformers of Diacetone Diperoxide (DADP)

Gas-phase infrared measurements of diacetone diperoxide (DADP) indicate a chair conformation with less than 5% of the predicted twist conformer. Vibrational frequencies are very similar to those previously measured in the solid state. Solution NMR measurements using 2D exchange spectroscopy (EXSY) a...

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Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2015-10, Vol.119 (40), p.10221-10228
Main Authors: Guo, Chunlei, Persons, John, Woodford, Jeffrey N, Harbison, Gerard S
Format: Article
Language:English
Subjects:
Chairs
Exchange
Infrared
Mathematical analysis
Nuclear magnetic resonance
Solvents
Spectroscopy
Thermochemistry
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Summary:Gas-phase infrared measurements of diacetone diperoxide (DADP) indicate a chair conformation with less than 5% of the predicted twist conformer. Vibrational frequencies are very similar to those previously measured in the solid state. Solution NMR measurements using 2D exchange spectroscopy (EXSY) also set a very low maximum limit on the equilibrium population of the twist conformer, with a room-temperature free-energy difference in excess of 14.5 kJ/mol. These experimental results are in accord with high-level quantum calculations incorporating full thermochemistry and solvation effects, which indicate a free-energy difference in the range of 14.7–17.5 kJ/mol in polar solvents.
ISSN:1089-5639
1520-5215
DOI:10.1021/acs.jpca.5b07074