Premium
CF 3 : An Electron‐Withdrawing Substituent for Aromatic Anion Acceptors? “Side‐On” versus “On‐Top” Binding of Halides
Author(s) -
Albrecht Markus,
Yi Hai,
Köksal Okan,
Raabe Gerhard,
Pan Fangfang,
Valkonen Arto,
Rissanen Kari
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201600249
Subject(s) - chemistry , substituent , halide , ion , ring (chemistry) , polarizability , aromaticity , hydrogen bond , trifluoromethyl , crystallography , side chain , computational chemistry , stereochemistry , inorganic chemistry , molecule , organic chemistry , alkyl , polymer
Abstract The ability of multiple CF 3 ‐substituted arenes to act as acceptors for anions is investigated. The results of quantum‐chemical calculations show that a high degree of trifluoromethyl substitution at the aromatic ring results in a positive quadrupole moment. However, depending on the polarizability of the anion and on the substitution at the arene, three different modes of interaction, namely Meisenheimer complex, side‐on hydrogen bonding, or anion–π interaction, can occur. Experimentally, the side‐on as well as a η 2 ‐type π‐complex are observed in the crystal, whereas in solution only side‐on binding is found.