Molecular geometry as a source of chemical information. 3. How H-bonding affects aromaticity of the ring in the case of phenol and p-nitrophenol complexes: a B3LYP/6-311+G study

Tadeusz M Krygowski; Joanna E Zachara; Halina Szatylowicz

doi:10.1021/jo049245a

Molecular geometry as a source of chemical information. 3. How H-bonding affects aromaticity of the ring in the case of phenol and p-nitrophenol complexes: a B3LYP/6-311+G study

J Org Chem. 2004 Oct 15;69(21):7038-43. doi: 10.1021/jo049245a.

Authors

Tadeusz M Krygowski¹, Joanna E Zachara, Halina Szatylowicz

Affiliation

¹ Department of Chemistry, Warsaw University, Pasteura 1, 02-093 Warsaw, Poland.

PMID: 15471450
DOI: 10.1021/jo049245a

Abstract

Molecular geometries of phenol and p-nitrophenol (ArOH) interacting with fluoride were optimized at the B3LYP/6-311+G level of theory taking as constraints the planarity of the systems and the linearity of the O...H...F moiety. For p-nitrophenol complexes, the substituent effect stabilization energy (SESE) was computed, and for all systems aromaticity indices, HOMA, and out-of-plane components of NICS(1) and NICS(1)(zz)() were calculated. SESE values depend strongly on the O...F distance, the same as both aromaticity indices. Variation in HOMA values for the studied ArOH...F(-) complexes is within the range of 0.55 to approximately 1.0 and for NICS(1)(zz)() between -12 and -26 ppm. It was also found that a decrease in aromaticity is well correlated with the variations of C-O bond length.