6533b835fe1ef96bd129f19a
RESEARCH PRODUCT
Phosphine-diène and Salicylamidines ligands : coordination chemistry, catalysis and therapy
Florian Chotardsubject
Arène-ruthéniumCatalyse[CHIM.COOR] Chemical Sciences/Coordination chemistryCatalysisAmidineROPChimie de coordinationDièneCoordination chemistrySchiff baseBase de SchiffArene-rutheniumDieneAza-dipyrromethenePLAThérapie[CHIM.COOR]Chemical Sciences/Coordination chemistryTherapyATRAAza-dipyrrométhènePhosphinedescription
The subject of this thesis concerns the development of new ligands, their coordination chemistry, and the synthesis of the corresponding metal complexes for catalysis and therapy.The first part of this work relates to the synthesis of diene-phosphine ligands, their saturated analogs, and the corresponding arene-ruthenium complexes. Arene decoordination allows the formation of a cationic bimetallic complex where the ligand is diène-η4/κ-P coordinated to the ruthenium. These complexes have been applied to atom transfer radical addition (ATRA) of CCl4 to styrene. When harsh reaction conditions are used, the superiority of the “diene” complexes is highlighted comparing to saturated analogs.The second part concerns the development of new Schiff base analogs: the “salicylamidines”. Several ligand generations have been obtained following different synthetic paths. They have been used for metal coordination, and are especially well-suited for the formation of zinc and aluminium complexes. Some of the compounds have been applied to ring opening polymerization (ROP) of lactides, and demonstrated good activity.The last part reports on the synthesis and assessment of metal-based anticancer agents. Some phosphine-gold and phosphine-ruthenium complexes have been synthesized and tested for their antiproliferative activity on several cancer cell lines. The phosphine-gold complexes showed impressive activities, better than cisplatine. Activity of phosphine-ruthenium is strongly influenced by the nature of the arene, ethyl benzoate derivatives are significantly more cytotoxic than p-cymene ones. Titanium and zirconium complexes with aza-dipyrromethene ligand were synthesized. Preliminary photophysical study was performed and indicated fluorescence. Their anticancer properties were assessed, and they are only poorly cytotoxic.
year | journal | country | edition | language |
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2017-09-29 |