Iminopropadienones, RN=C=C=C=O: Theory and experiment

Mosandl T., Stadtmuller S., Wong M.W. and Wentrup C. (1994) Iminopropadienones, RN=C=C=C=O: Theory and experiment. Journal of Physical Chemistry, 98 4: 1080-1086.

Author Mosandl T.
Stadtmuller S.
Wong M.W.
Wentrup C.
Title Iminopropadienones, RN=C=C=C=O: Theory and experiment
Journal name Journal of Physical Chemistry   Check publisher's open access policy
ISSN 0022-3654
Publication date 1994
Sub-type Article (original research)
Volume 98
Issue 4
Start page 1080
End page 1086
Total pages 7
Subject 1606 Political Science
Abstract Ab initio molecular orbital calculations at the MP2/6-31G* level have been used to examine the structures and infrared spectra of a new class of compounds, the iminopropadienones, RN=C=C=C=O (R = H, CH3, and Ph). The agreement between calculated and experimental IR spectra of PhNCCCO, Ph15NCCCO, and PhNCC13CO is excellent. Inclusion of electron correlation is found to be important for the correct prediction of the relative intensities of the cumulenic stretching vibrations. All three iminopropadienones are predicted to have a slightly bent NCCCO backbone (∠CCC ≈ 176°). As with carbon suboxide, these cumulenes are calculated to have an extremely flat CCC bending potential. The parent compound, HNCCCO (4a) is calculated to be thermodynamically stable toward dissociations into (i) HNCC + CO, (ii) HNC + CCO, (iii) HN + CCCO, and (iv) H• + NCCCO•. Rearrangement of 4a to the more stable cyanoketene isomer requires a sizeable barrier of 402 kJ mol-1 [G2(MP2)]. The calculated stability of 4a is consistent with its experimental observation in neutralization-reionization mass spectrum. The adiabatic ionization energy and heat of formation of HNCCCO are predicted to be 9.51 eV and 175 kJ mol-1, respectively.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown

Document type: Journal Article
Sub-type: Article (original research)
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