Pascal Guillo
Development of new ruthenium based catalysts for oxidation reaction: Towards photocatalytic systems
Published on 20 October 2010
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Thesis presented October 20, 2010
Abstract:
This thesis deals with the development of new homo and heterodinuclear ruthenium based complexes taking advantage of interesting properties of ruthenium polypyridinyl complexes: 1) the chirality of octahedral complexes, 2) their photophysical properties and 3) their catalytic properties for oxidation reactions.
At first, with the objective to use chiral properties of tris-diimine ruthenium complexes in asymmetric catalysis, modified manganese salen complexes constituted by the assembly of a ruthenium and Mn- or Zn-salen fragments were synthesized and fully characterized. More particularly, in the case of one of the Ru-Mn complexes a very efficient electron transfer has been also observed from the excited state of the ruthenium to the manganese.
In the second part of the thesis, the photosensitive and catalytic properties of ruthenium complexes were both associated within a unique complex. Two chromophore-catalyst dyad families were synthesized and fully characterized. Both of them showed high abilities to convert sulfides into sulfoxides under light exposure, using water as the only source of oxygen atom and a Co(III) salt as electron acceptor.
In the context of sustainable development, we have shown that the association of a photosensitizer and solar energy allows soft conditions to perform oxidation reactions.
Keywords:
Catalysis, ruthenium complexes, manganese salen complexes, photocatalysis, electron transfer, oxidation
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