Chemical and electrochemicalsynthesis of paramagnetic alkine complexes their applications in catalysis and organic synthesis

Lines connect the coordinator with its partners.

Project objective

Research objectives and content This proposal seeks support for a study of redox-generated alkyne radicals, particularly of the Group 6 metals, Co and Rh(II). The aims of this work are: -to synthesise a wide range of paramagnetic alkyne complexes -to exploit their chemical reactivity in stoichiometric and catalysed organometallic and organic synthesis -to devise clean and selective electrosyntheses based on alkyne radical as intermediates. -to initiate a study of aqueous organometallic electrochemistry. The new work will be based on complementary chemical and electrochemical studies. On basis of voltametry (giving the potentials at which the diamagnetic precursors are oxidised or reduced), methods forthe systematic generation (and isolation where possible) of the radicals will be devised. The potentials of substrate and chemical redox reagent will be matched on the basis of a recent compilation of data. Such radicals will also be generated electrolytically, at potentials chosen on the basis of voltammetry. The chemical reactivity of the radicals will be explored as outlined above. Throughout, all new species will be characterised spectroscopically (IR, NMR, etc.) and structurally X-ray structural and ESR spectroscopic studies of the paramagnetic complexes will be important in defining electronic structure. Where possible, reactive intermediates will be characterised by spectroelectrochemistry and the kinetics and mechanisms of radical reactions will be quantified by electrochemical methods. Training content (objective, benefit and expected impact) Electrochemistry may be used to gain mechanistic and quantitative informations on the reactivity of organometallic transient intermediates. These intermediates seem particularly suited to the study of electron transfer (ET) catalytic processes. This proposal offers perspectives in Homogeneous Catalysis due to the possibility of explaining the mechanisms of many catalytic reactions. Links with industry / industrial relevance (22)

Original text from CORDIS.

Participants

• UNIVERSITY OF BRISTOL · BRISTOL, CLIFTONCoordinatorUnited Kingdom

Links

• View on CORDIS