Electron interaction with copper(II) carboxylate compounds

In the present study we have performed electron collision experiments with copper carboxylate complexes: [Cu2(t-BuNH2)2(µ-O2CC2F5)4], [Cu2(s-BuNH2)2(µ-O2CC2F5)4], [Cu2(EtNH2)2(µ-O2CC2F5)4], and [Cu2(µ-O2CC2F5)4]. Mass spectrometry was used to identify the fragmentation pattern of the coordination compounds produced in crossed electron - molecular beam experiments and to measure the dependence of ion yields of positive and negative ions on the electron energy. The dissociation pattern of positive ions contains a sequential loss of both the carboxylate ligands and/or the amine ligands from the complexes. Moreover, the fragmentation of the ligands themselves is visible in the mass spectrum below m/z 140. For the studied complexes the metallated ions containing both ligands, e.g., Cu2(O2CC2F5)(RNH2)+, Cu2(O2CC2F5)3(RNH2)2+ confirm the evaporation of whole complex molecules. A significant production of Cu+ ion was observed only for [Cu2(µ-O2CC2F5)4], a weak yield was detected for [Cu2(EtNH2)2(µ-O2CC2F5)4] as well. The dissociative electron attachment processes leading to formation of negative ions are similar for all investigated molecules as the highest unoccupied molecular orbital of the studied complexes has Cu-N and Cu-O antibonding character. For all complexes, formation of the Cu2(O2CC2F5)4-• anion is observed together with mononuclear DEA fragments Cu(O2CC2F5)3-, Cu(O2CC2F5)2- and Cu(O2CC2F5)-•. All dominant DEA fragments of these complexes are formed through single particle resonant processes close to 0 eV.