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

被引：9

作者：

Cox, Hazel ^{[1
]}

Norris, Caroline ^{[1
]}

Wu, Guohua ^{[2
]}

Guan, Jingang ^{[1
]}

Hessey, Stephen ^{[2
]}

Stace, Anthony J. ^{[2
]}

机构：

[1] Univ Sussex, Dept Chem & Biochem, Brighton BN1 9QJ, E Sussex, England

[2] Univ Nottingham, Dept Phys Chem, Sch Chem, Nottingham NG7 2RD, England

来源：

DALTON TRANSACTIONS | 2011年 / 40卷 / 42期

基金：

英国工程与自然科学研究理事会;

关键词：

COLLISION-INDUCED DISSOCIATION; MAIN-GROUP THERMOCHEMISTRY; METAL-IONS; NONCOVALENT INTERACTIONS; BINDING-ENERGIES; COMPLEXES; COORDINATION; MOLECULES; PYRIDINE; WATER;

D O I：

10.1039/c1dt10769k

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

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 H2O, 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.

引用

页码：11200 / 11210

页数：11

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