Evidence of zinc superoxide formation in the gas phase: Comparisons in behaviour between ligated Zn(I/II) and Cu(I/II) with regard to the attachment of O2 or H2O

Singly and doubly charged atomic ions of zinc and copper have been complexed with pyridine and held in an ion trap. Complexes involving Zn(II) and Cu(I) (3d10) display a strong tendency to bind with H2O, whilst the Zn(I) (3d104s1) complexes exhibit a strong preference for the attachment of O2. DFT calculations show that this latter result can be interpreted as internal oxidation leading to the formation of superoxide complexes, [Zn(II)O2-](pyridine)n, in the gas phase. The calculations also show that the oxidation of Zn(I) to form Zn(II)O2- is promoted by a mixing of the occupied 4s and vacant 4p orbitals on the metal cation, and that this process is facilitated by the presence of the pyridine ligands.