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EPSRC Reference: GR/K16135/01
Title: EXTNS OF THE COORD CHEM OF AMAVADIN; N-HYDROXYCARBOXYLATE LIGANDS AS OXO-GROUP EQUIV WITH CHIRAL SELECTIVITY
Principal Investigator: Garner, Professor C D
Other Investigators:
Collison, Dr D
Researcher Co-Investigators:
Project Partners:
Department: Chemistry
Organisation: Victoria University of Manchester, The
Scheme: Standard Research (Pre-FEC)
Starts: 31 March 1996 Ends: 30 March 1999 Value (£): 6,246
EPSRC Research Topic Classifications:
Biological & Medicinal Chem.
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Summary on Grant Application Form
This investigation derives from the structure and reactivity established for the natural product Amavadin, which comprises a 1:2 complex of vanadium (IV) with the ligand S, S-2-hydroxyiminopropionic acid (HIDPAH3). Each ligand binds through two carboxylate groups and a deprotonated N-hydroxy function to give two mutually trans n2-N-O groups, approximately staggered by 90, above and below a roughly square planar arrangement of oxygen atoms. The structural and spectroscopic properties of several different diastereomers of [V(HIDPA)2]n-, n=2 or 1, have shown an electronic/bonding equivalence between two trans h2-N-O groups and one oxo-group. We have already justified this view chemically by the successful synthesis and characterisation of [D-Mo(R,R-HIDPA)(R,S-HIDPA)] - and its enantiomer. The complexes containing two HIDPA ligands have a rich reversible redox chemistry, five chiral centres, and show novel reactivity. The programme seeks to build these results: 9I) to explore the chemistry with other metals; (ii) to characterise the geometry and electronic structure of the complexes using a wide range of modern methodologies; (iii) to develop the reactivity of the systems, monitored by the essential probes of circular dichroism spectroscopy and electrochemistry, to enquire whether the new molecules can serve as catalysts in asymmetric syntheses.
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