Synthesis, purification, and characterization of tetraphosphine ligands

Abstract : : Recent developments in green and sustainable science require more powerful, sophisticated and tunable catalysts. Bimetallic catalysts contain two or more sites for the activation of substrates and, under optimal circumstances, can allow cooperative activation of reacting substrates on neighboring metal centers. A number of backbones, designed specifically to generate exclusively bimetallic complexes have previously been developed around methanodibenzodioxocin and benzofurobenzofuran scaffolds, including a number of ligands that act as monophosphine donors to two different metal centers. These ligands generate dinuclear species reliably, but the resulting coordination modes are unpredictable. This work presents the synthesis of tetraphosphine ligands, wherein chelating arms are available to coordinate each of the two metal centers. The synthesis involves preparation of 4,8-bis(sec-phosphines) of rac- 6,12-methano-12H-dibenzo[l,3] dioxocins and their conversion into doubly chelating phosphines through the elaboration of each sec- phosphine functionality into the corresponding di(R)phosphinopropyl derivatives (R= Ph, Cy). A preliminary coordination chemistry study indicates that the tightly defined coordination environment provided by these rigid binucleating tetraphosphine ligands under study allowed bimetallic complexes of PdII, PtII to be prepared, in which each of the two chelating arms molecule coordinates to one metal. Finally outline studies on the use of the tetraphosphine ligands as supports for hydroformylation chemistry were performed. The current results do not yet allow cooperative behavior between the two metal centers to be definitively established.
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  • HAL Id : tel-01631221, version 1

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Deniz Cevik. Synthesis, purification, and characterization of tetraphosphine ligands. Other. Université Paris-Saclay, 2017. English. ⟨NNT : 2017SACLX026⟩. ⟨tel-01631221⟩

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