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Basicity of the polydentate captodative aminoenones. Ab initio , DFT, and FTIR study
Author(s) -
Kondrashov E. V.,
Oznobikhina L. P.,
Aksamentova T. N.,
Chipani. N.,
Romanov A. R.,
Rulev A. Yu.
Publication year - 2016
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3532
Subject(s) - chemistry , natural bond orbital , ab initio , heteroatom , density functional theory , fourier transform infrared spectroscopy , denticity , double bond , computational chemistry , ab initio quantum chemistry methods , hydrogen bond , proton affinity , infrared spectroscopy , crystallography , organic chemistry , molecule , crystal structure , ring (chemistry) , ion , physics , protonation , quantum mechanics
Electron donating ability of the oxygen, nitrogen, and carbon atoms of captodative aminoenones R'CH = C(NR 2 )EWG, EWG = CHO, C(O)Me, C(O)CF 3 , 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.