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Effect of fluorine substitution on the proton transfer barrier in malonaldehyde. A density functional theory study

✍ Scribed by Fabio Pichierri

Publisher: Elsevier Science
Year: 2003
Tongue: English
Weight: 264 KB
Volume: 376
Category: Article
ISSN: 0009-2614
DOI: 10.1016/s0009-2614(03)01117-5

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✦ Synopsis

The effect of fluorine substitution on the proton transfer barrier (DE PT ) of malonaldehyde (1) has been investigated with the aid of density functional theory (DFT) calculations carried out at the B3LYP/cc-pVTZ level of theory. The results indicate that fluorine substitution in 1 increases the energy barrier for intramolecular proton transfer, which correlates linearly with both the HB distance and the O-H bond stretching frequency. The origin of this structureenergy correlation was investigated by performing a topological analysis of the electron density with BaderÕs theory of atoms in molecules (AIM). AIM theory indicates that H-by-F substitution in 1 has the effect to decrease the electron density of its intramolecular HB. This implies that conjugation effects are operative within the enolone fragment of 1.

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