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Mechanistic Studies on the Water-Oxidizing Reaction of Homogeneous Manganese-Based Catalysts: Isolation and Characterization of a Suggested Catalytic Intermediate
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, Molecular Biomimetics.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Photochemistry and Molecular Science, Molecular Biomimetics.
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2011 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 50, no 8, 3425-3430 p.Article in journal (Refereed) Published
Abstract [en]

The synthesis, isolation, and characterization of two high-valent manganese dimers with isomeric ligands are reported. The complexes are synthesized and crystallized from solutions of low-valent precursors exposed to tert-butyl hydroperoxide. The crystal structures display centrosymmetric complexesconsisting of Mn2 IV,IV(μ-O)2 cores, with one ligand coordinating to each manganese. The ligands coordinate with the diaminoethane backbone, the carboxylate, and one of the two pyridines, while the second pyridine is noncoordinating. The activity of these complexes, under water oxidation conditions, is discussed in light of a proposed mechanism for water oxidation, in which this type of complexes have been suggested as a key intermediate.

Place, publisher, year, edition, pages
2011. Vol. 50, no 8, 3425-3430 p.
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:uu:diva-108524DOI: 10.1021/ic102336aISI: 000290457700034PubMedID: 21428420OAI: oai:DiVA.org:uu-108524DiVA: diva2:236180
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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Supervisors
Available from: 2009-10-15 Created: 2009-09-21 Last updated: 2009-10-15Bibliographically approved

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Berggren, GustavThapper, AndersHuang, PingStyring, Stenbjörn

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