Electronic structures of cyclometalated palladium complexes in the higher oxidation states
Bao N Nguyen1, Luis A Adrio, Tim Albrecht
1Department of Chemistry, Imperial College London, Exhibition Road, South Kensington, London SW7 2AZ, UK. mimi.hii@imperial.ac.uk.
Abstract:
The electronic and redox properties of a series of cyclometalated Pd complexes with oxidation states of +2, +3 and +4 were examined using a range of currently available spectroscopic and electrochemical techniques. Changes in metal-ligand bond lengths were established by X-ray crystallography and correctly predicted by DFT calculations, from which the frontier orbitals and partial atomic charges can be obtained. X-ray absorption spectroscopy (XAS) revealed interesting XANES features that suggest a synergistic relationship between metal-ligand interactions. The electrochemical study of the Pd(ii) dimer was found to contain two sequential oxidative potentials indicative of a weak metal-metal interaction.
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