Competing radical and non-radical pathways for the decomposition of LFeII(H2O2) complexes:: a density functional study

被引：13

作者：

Anastasi, Anna E.

Lienke, Achim

Comba, Peter

Rohwer, Heidi

McGrady, John E. ^{[1
]}

机构：

[1] Univ Glasgow, Dept Chem, WestCHEM, Glasgow G12 8QQ, Lanark, Scotland

[2] Heidelberg Univ, Inst Anorgan Chem, D-69120 Heidelberg, Germany

[3] Unilever Res Labs, NL-3133 AT Vlaardingen, Netherlands

[4] Univ York, Dept Chem, York YO10 5DD, N Yorkshire, England

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2007年 / 01期

关键词：

density functional calculations; oxido ligands; O-O activation; electronic structure; transition states;

D O I：

10.1002/ejic.200600786

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Density functional theory has been used to explore the mechanism of hydrogen peroxide decomposition when coordinated to a bispidone iron(II) complex. Two quite distinct pathways are identified, one involving O-O bond homolysis followed by a "rebound" hydrogen atom abstraction, the other involving proton transfer followed by O-O bond heterolysis. A water molecule in the second coordination sphere plays a key role in both pathways. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weirtheint, Germany, 2007).

引用

页码：65 / 73

页数：9

共 51 条

[1] Fe(II) and Fe(III) mononuclear complexes with a pentadentate ligand built on the 1,3-diaminopropane unit.: Structures and spectroscopic and electrochemical properties.: Reaction with H2O2 [J].