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Formation of stoichiometrically O-18-labelled oxygen from the oxidation of O-18-enriched water mediated by a dinuclear manganese complex: a mass spectrometry and EPR study
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Photochemistry and Molecular Science.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Photochemistry and Molecular Science.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Photochemistry and Molecular Science.
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2008 (English)In: Energy & Environmental Science, ISSN 1754-5692, E-ISSN 1754-5706, Vol. 1, no 6, 668-676 p.Article in journal (Refereed) Published
Abstract [en]

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.

Place, publisher, year, edition, pages
2008. Vol. 1, no 6, 668-676 p.
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-108518DOI: 10.1039/b811806jISI: 000263888600006ISBN: 1754-5692 (print)OAI: oai:DiVA.org:uu-108518DiVA: diva2:236170
Available from: 2009-09-21 Created: 2009-09-21 Last updated: 2017-12-13
In thesis
1. Mimicking Nature – Synthesis and Characterisation of Manganese Complexes of Relevance to Artificial Photosynthesis
Open this publication in new window or tab >>Mimicking Nature – Synthesis and Characterisation of Manganese Complexes of Relevance to Artificial Photosynthesis
2009 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The development of efficient catalyst for water oxidation is of paramount importance to artificial photosynthesis, but before this can be achieved a deeper understanding of this reaction is essential. In nature this reaction occurs in a tetranuclear Mn-cluster which serves as the work-horse of oxygenic photosynthesis. This thesis summarises my efforts at developing molecular systems capable of mimicking this complex employing a biomimetic approach.

Three different approaches towards this goal are described here-in. The first section describes a screening study, in which a number of manganese complexes were tested to see whether or not they were capable of catalysing the formation of dioxygen when treated with different oxidants (Papers I). For those reactions in which dioxygen formation was observed the reactions were repeated in labelled water and the incorporation of labelled O-atoms was studied by mass spectrometry. This allowed us to determine to what extent water was the source of the evolved dioxygen (Papers II-III).

In Chapter three a reported catalyst and a derivative thereof is studied in depth. The influence of changes to the ligand on the oxygen–oxygen bond forming reaction could unfortunately not be reliably addressed, because of the instability of the complexes under “catalytic” conditions. Nevertheless, the study allowed us to revise the “carboxylate shift”-mechanism suggested in the literature (Papers IV-V).

Chapter four describes the continuation of my work on ligands featuring the carboxylate ligand motif first introduced in Chapter three. In this study ligands containing multiple binding pockets were designed and synthesised (Paper VI).

A better understanding of the mechanism in the natural water oxidising enzyme will facilitate the design of biomimetic complexes, this is discussed in Chapter five. In this work model complexes (Paper VII) are used to study the mechanism by which natures own water oxidising catalyst performs this reaction.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2009. 101 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 674
Keyword
Manganese, biomimetic, artificial photosynthesis, water splitting, homogeneous catalysis
National Category
Other Basic Medicine
Research subject
Physical Chemistry
Identifiers
urn:nbn:se:uu:diva-108526 (URN)978-91-554-7614-4 (ISBN)
Public defence
2009-11-06, Polhemsalen, Ångströmslaboratoriet, Lägerhyddsvägen 1, Uppsala, 10:00 (English)
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Available from: 2009-10-15 Created: 2009-09-21 Last updated: 2009-10-15Bibliographically approved

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Berggren, GustavThapper, AndersStyring, Stenbjörn

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