Table of Contents
ISRN Spectroscopy
Volume 2013, Article ID 640896, 13 pages
Research Article

C–HF Hydrogen Bond and Integral Intensities of Vinyl C–H Vibtations in Push-Pull β-Dimethylaminotrifluoromethyl Ketone and Its Deuterated Analog

Institute of Bioorganic Chemistry and Petrochemistry, National Academy of Sciences of Ukraine, ul. Murmanska 1, Kiev 02094, Ukraine

Received 22 August 2012; Accepted 26 September 2012

Academic Editors: M. Mączka and S. Pandey

Copyright © 2013 Sergei Vdovenko et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.


The accurate analysis of infrared spectra (both wavenumbers and intensities) of (E)-4-(dimethylamino)-1,1,1-trifluorobut-3-en-2-one (DMTBN) and (E)-4-(hexadeutero-dimethylamino)-1,1,1-trifluorobut-3-en-2-one (d6-DMTBN) revealed that besides intramolecular hydrogen bond in the (EE) conformer, these enaminoketones form cyclic dimers between the (EZ) and (EE) conformers due to intermolecular hydrogen bonds, namely, O=C and . Evaluation of constant and enthalpy of formation of these H-bonds revealed that O=C bond has greater and more negative than bond (cf. 214.4 M−1, −21.7 kJ M−1dm3, and 16.4 M−1, −6.7 kJ M−1dm3, resp.). Consequently, stronger H-bond O=C is formed in the first place, whereas weaker H-bond is formed afterward. Moreover, formation of intermolecular hydrogen bond has influence on C–F vibrations, but analysis of this influence must take into account the fact that these vibrations in some cases are coupled with . True enthalpy of the equilibrium (EZ)(EE) is positive (25.3 kJ M−1dm3), thus confirming results of DFT calculations, according to which the (EZ) conformer is more stable than the (EE) one.