title: Anion-pi interactions-interactions between benzo-crown ether metal cation complexes and counter ions.
abstract: The loss of X(.) radical from [M + Cu + X](+) ions (copper reduction) has been studied by the so called in-source fragmentation at higher cone voltage (M = crown ether molecule, X(-) = counter ion, ClO(4)(-), NO(3)(-), Cl(-)). The loss of X(.) has been found to be affected by the presence/lack of aromatic ring poor/rich in electrons. Namely, the loss of X(.) occurs with lower efficiency for the [NO(2)-B15C5 + Cu + X](+) ions than for the [B15C5 + Cu + X](+) ions, where NO(2)-B15C5 = 3-nitro-benzo-15-crown-5, B15C5 = benzo-15-crown-5. A reasonable explanation is that Anion-pi interactions prevent the loss of X(.) from the [NO(2)-B15C5 + Cu + X](+) ions. The presence of the electron-withdrawing NO(2) group causes the aromatic ring to be poor in electrons and thus its enhances its interactions with anions. For the ion containing the aromatic ring enriched in electrons, namely [NH(2)-B15C5 + Cu + ClO(4)](+) where NH(2)-B15C5 = 3-amino-benzo-15-crown-5, the opposite situation has been observed. Because of Anion-pi repulsion the loss of X(.) radical proceeds more readily for [NH(2)-B15C5 + Cu + X](+) than for [B15C5 + Cu + X](+). Iron reduction has also been found to be affected by Anion-pi interactions. Namely, the loss of CH(3)O(.) radical from the ion [B15C5 + Fe + NO(3) + CH(3)O](+) proceeds more readily than from [NO(2)(-)B15C5 + Fe + NO(3) + CH(3)O](+).
authors.affiliation: Faculty of Chemistry, Adam Mickiewicz University, Poznań, Poland. franski@main.amu.edu.pl
authors.forename: Rafał
authors.initials: R
authors.lastname: Frański
authors.forename: Błazej
authors.initials: B
authors.lastname: Gierczyk
authors.forename: Grzegorz
authors.initials: G
authors.lastname: Schroeder