Formation of stoichiometrically 18O-labelled oxygen from the oxidation of 18O-enriched water mediated by a dinuclear manganese complex - a mass spectrometry and EPR study

被引：93

作者：

Beckmann, Katrin ^{[1
]}

Uchtenhagen, Hannes ^{[2
]}

Berggren, Gustav ^{[2
]}

Anderlund, Magnus F. ^{[2
]}

Thapper, Anders ^{[2
]}

Messinger, Johannes ^{[1
]}

Styring, Stenbjorn ^{[2
]}

Kurz, Philipp ^{[2
,3
]}

机构：

[1] Max Planck Inst Bioanorgan Chem, D-45470 Mulheim, Germany

[2] Uppsala Univ, Dept Photochem & Mol Sci, Angstrom Lab, S-75120 Uppsala, Sweden

[3] Univ Kiel, Inst Anorgan Chem, D-24118 Kiel, Germany

来源：

ENERGY & ENVIRONMENTAL SCIENCE | 2008年 / 1卷 / 06期

关键词：

D O I：

10.1039/b811806j

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Oxygen formation was detected for the oxidations of various multinuclear manganese complexes by oxone (HSO5-) in aqueous solution. To determine to what extent water was the source of the evolved O-2, (H2O)-O-18 isotope-labelling experiments coupled with membrane inlet mass spectrometry (MIMS) were carried out. We discovered that during the reaction of oxone with [Mn-2(OAc)(2)(bpmp)](+) (1), stoichiometrically labelled oxygen (O-18(2)) was formed. This is the first example of a homogeneous reaction mediated by a synthetic manganese complex where the addition of a strong chemical oxidant yields O-18(2) with labelling percentages matching the theoretically expected values for the case of both O-atoms originating from water. Experiments using lead acetate as an alternative oxidant supported this finding. A detailed investigation of the reaction by EPR spectroscopy, MIMS and Clark-type oxygen detection enabled us to propose potential reaction pathways.

引用

页码：668 / 676

页数：9

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