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Development of metal complexes for water oxidation
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In an artificial version of photosynthesis, sunlight and water are used to produce fuels. Our research focuses on the bottleneck in this process, the photooxidation of water. In the course of developing a water oxidation catalyst, a number of metal complexes have been synthesised, characterised, and studied for catalytic activity. Three of them are dinuclear complexes (Ru, Co and Cu) of 2,6-bis[(2-hydroxybenzyl)-(2-pyridylmethyl)aminomethyl]-4-methylphenol (H3bbpmp). The fourth is a dimeric Ru complex with a ligand containing imidazole and phenol motifs. Additionally, a dinuclear Mn complex with a ligand that contains benzimidazoles and carboxylates coordinating to the metal atoms was also developed. This Mn complex was then covalently linked to [Ru(bpy)3]2+-type photosensitisers, resulting in three different bimetallic dyads. Finally, a dinuclear Fe complex containing the same ligand as the dinuclear Mn complex was synthesised.

The potential of the three H3bbpmp complexes as catalysts for oxidation of organic compounds was investigated and it was found that the Ru complex catalyses the oxidation of alcohols to the corresponding ketone or aldehyde using (diacetoxyiodo)benzene as oxidant. The Co complex functions as an electron transfer mediator in a coupled catalytic system for allylic oxidation using oxygen gas. The oxidation of 3,5-di-tert-butylcatechol to the corresponding ortho-quinone with oxygen gas using the copper complex proved that it can be considered as a model of catecholase. The dimeric Ru complex and the dinuclear Mn and Fe complexes proved to catalyse water oxidation when employing stoichiometric amounts of the oxidant [Ru(bpy)3](PF6)3. Furthermore, using [Ru(bpy)2(deeb)](PF6)2 as photosensitiser together with Na2S2O8 as sacrificial electron acceptor in aqueous phosphate buffer at pH = 7.2, photochemical water oxidation was demonstrated. The bimetallic dyads however, did not show catalytic activity for the oxidation of water.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University , 2013. , 68 p.
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-89075ISBN: 978-91-7447-663-7 (print)OAI: oai:DiVA.org:su-89075DiVA: diva2:615915
Public defence
2013-05-17, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12, Stockholm, 10:00
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 4: Manuscript. Paper 5: Manuscript.

Available from: 2013-04-25 Created: 2013-04-10 Last updated: 2013-04-16Bibliographically approved
List of papers
1. Synthesis and characterization of oligonuclear Ru, Co, and Cu oxidation catalysts
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2010 (English)In: European Journal of Inorganic Chemistry, ISSN 1434-1948, E-ISSN 1099-0682, no 34, 5462-5470 p.Article in journal (Refereed) Published
Abstract [en]

In this work, we report the preparation and crystal structures of three new oligonuclear complexes, Ru-2(bbpmp)(mu-OAc)(3) (4), [Co-2(bbpmp)(mu-OAc)(mu-OMe)](PF6) (5), [Cu-4(Hbbpmp)(2)(mu-OAc)(H2O)(2)](OAc)(PF6)(2) (6) {H(3)bbpmp = 2,6-bis[(2-hydroxybenzyl)-(2-pyridylmethyl)aminomethyl]-4-methylphenol (3)}. The structures of the complexes were determined by single-crystal X-ray diffraction. The oxidation states of ruthenium, cobalt and copper in the complexes are +3, +3 and +2, respectively. In 4 and 5, Ru-III and Co-III are coordinated to four oxygen and two nitrogen atoms in an octahedral geometry, while in 6, Cu-II adopts both octahedral (CuN2O4) and square-pyramidal (CuN2O3) geometry. The potential of the three complexes as oxidation catalysts has been investigated.

Keyword
O-O activation, Homogeneous catalysis, N, O ligands, Oxidation
National Category
Inorganic Chemistry Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-50703 (URN)10.1002/ejic.201000758 (DOI)000285262900014 ()
Funder
Knut and Alice Wallenberg FoundationSwedish Research Council
Available from: 2010-12-30 Created: 2010-12-30 Last updated: 2013-04-15Bibliographically approved
2. Light-Induced Water Oxidation by a Ru-complex Containing a Bio-Inspired Ligand
Open this publication in new window or tab >>Light-Induced Water Oxidation by a Ru-complex Containing a Bio-Inspired Ligand
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2011 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 17, no 28, 7953-7959 p.Article in journal (Refereed) Published
Abstract [en]

The new Ru-complex 8 containing the bio-inspired ligand 7 was successfully synthesized and characterized. Complex 8 could efficiently catalyze water oxidation using CeIV and RuIII as chemical oxidants. More importantly, this complex has sufficiently low overpotential to utilize ruthenium polypyridyl-type complexes as photosensitizers.

Keyword
homogeneous catalysis, oxidation, photochemistry, ruthenium, water splitting
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-56884 (URN)10.1002/chem.201003702 (DOI)000293383300033 ()
Funder
Knut and Alice Wallenberg Foundation
Available from: 2011-04-28 Created: 2011-04-28 Last updated: 2017-12-11Bibliographically approved
3. Photosensitized water oxidation by use of a bioinspired manganese catalyst
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2011 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 50, no 49, 11715-11718 p.Article in journal (Refereed) Published
Keyword
homogeneous catalysis, manganese, N, O ligands, photocatalysis, water oxidation
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-65534 (URN)10.1002/anie.201104355 (DOI)000298084900028 ()
Funder
Knut and Alice Wallenberg FoundationEU, European Research Council
Available from: 2011-12-12 Created: 2011-12-12 Last updated: 2017-12-08Bibliographically approved
4. Synthesis and electron transfer processes in a new family of coupled Mn2–Ru complexes
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(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-89072 (URN)
Available from: 2013-04-10 Created: 2013-04-10 Last updated: 2013-04-15Bibliographically approved
5. Light-induced water oxidation by a dinuclear iron-based molecular catalyst
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(English)Manuscript (preprint) (Other academic)
Keyword
water oxidation catalysis
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-88157 (URN)
Available from: 2013-04-10 Created: 2013-03-07 Last updated: 2014-03-24

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