Hydroxyl group as a substituent with varying electronic properties: effect of strength of H-bonding on charge density changes in Ph-OH…F⁻ complexes.
Due to gradual and controlled changes of interatomic distances between heavy atoms in OH…F⁻ of C(6)H(5)OH…F⁻ systems it was possible to study the electronic structure evolution. Computation at B3LYP/6-311+G(d,p) level of theory was performed for this purpose. Changes in charges at atoms and characteristics at bond critical points (BCPs) of the H-bond region and also in distant parts of the systems were investigated by means of natural bond orbitals (NBO) and atoms in molecules (AIM) analyses. It is shown that at the border line between partially covalent and non-covalent H-bonding (Espinosa et al. in J Chem Phys 117:5529, 2002; Grabowski et al. in J Phys Chem B 110:6444, 2006) with the H…F interatomic distance ~1.8 Ǻ the hydrogen atom has the most positive charge. In addition, the change in the atomic charge values in the interacting region affects the phenyl ring properties. The decrease of the sum of atomic charges as well as of the aromaticity was noticed when the OH….F distance is shortened.
Szatyłowicz
Halina
H
Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland. halina@ch.pw.edu.pl
Krygowski
Tadeusz Marek
TM
Jezierska-Mazzarello
Aneta
A
D004581:Electronics; D005459:Fluorides / Q000737:chemistry; D006860:Hydrogen Bonding; D006878:Hydroxides / Q000737:chemistry*; D019800:Phenol / Q000737:chemistry*; D055672:Static Electricity
D006878:Hydroxides; D019800:Phenol; C031356:hydroxide ion; D005459:Fluorides
J Org Chem. 2005 Oct 28;70(22):8859-65
16238319
J Chem Inf Model. 2007 May-Jun;47(3):875-86
17444628
J Org Chem. 2004 Oct 15;69(21):7038-43
15471450
J Phys Chem A. 2006 Jun 8;110(22):7232-6
16737274
Chemistry. 2007;13(28):7996-8006
17607686
Chem Rev. 2005 Oct;105(10):3513-60
16218560
J Phys Chem B. 2006 Apr 6;110(13):6444-6
16570938
Annu Rev Phys Chem. 1997;48:511-44
9348662
Phys Rev B Condens Matter. 1988 Jan 15;37(2):785-789
9944570
J Phys Chem A. 2005 Jul 28;109(29):6532-9
16833999
Chem Rev. 2005 Oct;105(10):3482-512
16218559