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Content archived on 2024-05-07

Synthesis, characterisation and theoretical analysis of spin-stabilised unsaturated mo - iii - alkyl complexes as potential polyerisation catalysts for functionalised substrates


Research objectives and content
The release of spin-pairing energy has long been established as a critical factor in the reactivity of transition-metal coordination compounds. Only recently has this concept been extended to open-shell organometallic species. The proposed research will apply spin-stabilisation to the generation of 15-valence-electron molybdenum(III) alkyl complexes under mild conditions. These unsaturated, spin-quartet species will possess an open coordination site cis to the alkyl ligand, a requirement for polymerisation catalysts. The electronic and steric properties of the molybdenum(III) alkyl complexes will be optimised by appropriate modification of the ancillary ligands. Advanced computational techniques will be applied to resolve spin-state an mechanistic questions as they arise. Mo-based polymerisation catalysts are expected to display a greater tolerance of function groups than early transition-metal metallocene catalysts, presenting the possibility of new materials derived from polymerisation (or co-polymerisation) of functionalised monomers. Training content (objective, benefit and expected impact)
The proposed research will provide insight into the effect of spin state in stabilising open-shell organometallic complexes. The unsaturated alkyl species formed in this manner will be assessed as potential polymerisation catalysts for functionalised monomers. This project will enable me to: (a) further develop my skills in the synthesis and characterisation of new, paramagnetic transition-metal complexes, (b) acquire direct experience with advanced computational techniques, and (c) learn the methodologies associated with transition-metal-catalysed polymerisation. Joining the research group of Prof. Poli at U. Bourgogne will allow me to pursue these goals in a single, integrated research project.
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6,Boulevard Gabriel 6
21000 DIJON

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