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.
Dalton Trans
; 40(42): 11200-10, 2011 Nov 14.
Article
em En
| MEDLINE
| ID: mdl-21901204
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.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Oxigênio
/
Teoria Quântica
/
Zinco
/
Água
/
Superóxidos
/
Cobre
/
Gases
Idioma:
En
Ano de publicação:
2011
Tipo de documento:
Article