1. No category

ICHAC-XI, International Conference on Heteroatom Chemistry
Caen (France), 14-19 June 2015
DYNAMIC BEHAVIOR OF THE Y-X---π INTERACTIONS (X, Y = F,
Cl, Br, AND I) IN BENZENE π SYSTEM, ELUCIDATED BY AIM-DFA
Yuji Sugibayashi, Satoko Hayashi, and Waro Nakanishi*
Department of Material Science and Chemistry, Faculty of Systems Engineering, Wakayama
University, 930 Sakaedani, Wakayama, 640-8510 Japan: nakanisi@sys.wakayama-u.ac.jp
Halogen bonds/interactions of the Y-X---π type are one of basic type of interactions in
chemistry. The type of interactions must have wide variety with the structural changes of the
π systems, the planar and bowl-type π systems, for example. Here, we clarified the dynamic and
static behavior of the Y-X-∗-π(C6H6) interactions (X, Y = Cl, Br,1 and I),
as a first step to clarify the whole picture of the interactions, where -∗emphasize the presence of bond critical points
Y
betqeen Y-X and benzene π system. AIM-DFA
X
(atoms-in-molecules dual functional analysis)2 is
applied to the interactions, which we proposed
recently.
Fig. 1 shows molecular graph for F-F-∗-
Y-X-∗-π inY-X---C6H6
(X, Y = F, Cl, Br, and I)
Hb(rc)
(au)
π(C6H6), where an F atom in F2 is connected to a
BCP of C-∗-C in C6H6 through a bond path.
0.0020
Molecular graphs of other halogen adducts are
similar to that in Fig. 1, although those for X-F-∗π(C6H6) (X = Cl, Br, and I) are something
0.0015
0.0010
different. Fig. 2 shows the AIM-DFA plots for YX-∗-π(C6H6) (X, Y = Cl, Br, and I). The treatment
0.0005
clarified that X-Y of F-F forms typical vdW
adduct, whereas X-Y of I-F gives typical HB,
although the F-I-∗-π(C6H6) interaction contains no
0.004
0.006
Hb(rc) – Vb(rc)/2 (au)
0.008
Fig. 2 AIM-DFA plots for π (C6H6)-∗-X-Y.
X-Y are shown in the figure.
covalency. Other interactions are classifed as vdW-type, although basis set system affect much
on the behavior. Datails will be didcused in the presentation.
1
2
Vasilyev, A. V.; Lindeman, S. V.; Kochi, J. K. New. J. Chem. 2002, 26, 582.
Nakanishi, W.; Hayashi, S.; Narahara, K. J. Phys. Chem. A 2009, 113, 10050; 2010, 114, 7423.