title: 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.
abstract: 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) (3d(10)) display a strong tendency to bind with H(2)O, whilst the Zn(I) (3d(10)4s(1)) complexes exhibit a strong preference for the attachment of O(2). DFT calculations show that this latter result can be interpreted as internal oxidation leading to the formation of superoxide complexes, [Zn(II)O(2)(-)](pyridine)(n), in the gas phase. The calculations also show that the oxidation of Zn(I) to form Zn(II)O(2)(-) 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.
authors: Department of Chemistry and Biochemistry, University of Sussex, Falmer, Brighton, UK BN1 9QJ.
authors: Hazel
authors: H
authors: Cox
authors: Caroline
authors: C
authors: Norris
authors: Guohua
authors: G
authors: Wu
authors: Jingang
authors: J
authors: Guan
authors: Stephen
authors: S
authors: Hessey
authors: Anthony J
authors: AJ
authors: Stace
mesh_terms: D003300:Copper / Q000737:chemistry*; D005740:Gases / Q000737:chemistry*; D058116:Lewis Acids / Q000737:chemistry; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry; D011789:Quantum Theory; D013481:Superoxides / Q000737:chemistry*; D014867:Water / Q000737:chemistry*; D015032:Zinc / Q000737:chemistry*
chemical_list: D005740:Gases; D058116:Lewis Acids; D008024:Ligands; D009942:Organometallic Compounds; D011725:Pyridines; D014867:Water; D013481:Superoxides; D003300:Copper; D015032:Zinc; C023666:pyridine; D010100:Oxygen