Basicity of the polydentate captodative aminoenones. Ab initio, DFT, and FTIR study

• Published in: Journal of physical organic chemistry Vol. 29; no. 6; pp. 288 - 298
• Main Authors: Kondrashov, E. V., Oznobikhina, L. P., Aksamentova, T. N., Chipanina, N. N., Romanov, A. R., Rulev, A. Yu
• Format: Journal Article
• Language: English
• Published: Bognor Regis Blackwell Publishing Ltd 01.06.2016; Wiley Subscription Services, Inc
• Subjects: Bond strength; captodative aminoenones; DFT/MP2/IR study; Fourier transforms; homodesmotic reactions; hydrogen bond; NBO analysis; proton affinity
• ISSN: 0894-3230; 1099-1395
• DOI: 10.1002/poc.3532

Electron donating ability of the oxygen, nitrogen, and carbon atoms of captodative aminoenones R'CH = C(NR2)EWG, EWG = CHO, C(O)Me, C(O)CF3, C(O)Ph was investigated using ab initio and Density Functional Theory (DFT) calculations, Natural Bond Analysis (NBO) analysis, and Fourier Transform InfraRed (FTIR) spectroscopy. The influence of both electron withdrawing group (EWG) and double bond substituents on the proton affinity of the basic centers, orbital interaction, as well as resonance stabilization energies between heteroatoms and double bonds are discussed. The results obtained are critically compared with the push–pull aminoenones. The comparison of experimental values ΔνOH and theoretical values of H‐bonding energy was used to determine the H‐complex type of aminoenone with phenol and the H‐bond strength. Copyright © 2016 John Wiley & Sons, Ltd. Electron donating ability of the oxygen, nitrogen, and carbon atoms of captodative aminoenones was investigated using ab initio and DFT calculations, NBO analysis, and FTIR spectroscopy. The influence of both EWG and double bond substituents on the proton affinity of the basic centers and the orbital interaction energies between heteroatoms and double bonds is discussed.