Construction of vanadium redox systems based on function design

• Applicant: Professor Dr. Dieter Rehder
• Subject Area: Inorganic Molecular Chemistry - Synthesis and Characterisation
• Term: from 2002 to 2004
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 5371460

We intend to synthesise and characterise vanadium complexes predominantly in the oxidation states IV and V, which are related to the active centres of vanadate-dependent haloperoxidases. In view of the similarities of the vanadium and molybdenum chemistries, vanadium-based model compounds of molybdenum-dependent oxo-transfer enzymes will be included. For this issue, ligands will be designed (in part by the Japanese counter-part) which allow to closely model the active sites with respect to structure and function. The envisaged ligands will contain three to five functionalities and at leat one chiral element. Among the funcionalities, an aromatic or imine nitrogen to model histidine binding, a thiolate to model cysteine binding, and oxygen functions (alkoxide, phenolate, carbosylate) will be present. The vanadium complexes will be designed so as to have available an accessible coordination site (coordination number five in a tetragonal-pyramidal or trigonal-bipyramidal array, or coordination number six with one of the ligand functions weakly bonded to vanadium). Characterisation will be carried out by multiple solution and solid state methods. Reaction kinetics and mechanistic aspects will be considered mainly by the Japanese groups.

• DFG Programme: Research Grants
• International Connection: Japan
• Participating Person: Professor Dr. Toshikazu Hirao