First-row transition-metal Schiff base complexes are of interest for their potential to act as chromophores for novel C-C bond forming schemes. A previously reported �Cr(II)� tripodal iminopyridine complex was demonstrated to be a Cr(III) ion combined with a ligand radical anion.1  DFT calculations predict that such ligand non-innocence is important for selective photo-activation of pi systems such as carbonyl- and imine-containing small molecules.  The V(II) analogue of the Cr(III) ligand radical anion is targeted for being isoelectronic with Cr(III) and possessing stronger absorption in the visible spectrum.  Several related Schiff base ligands that possess one or more open coordination sites are also being explored to allow substrate binding and achieve inner sphere electron transfer for photocatalysis.  The syntheses, crystal structures, redox potentials and electronic transitions of these complexes will be presented.1) McDaniel, A. M.; Rapp�, A. K.; Shores, M. P. Inorg. Chem. 2012 , 51, 12493-12502.

Investigation of vanadium Schiff base complexes as chromophores for photocatalysis

248th National Meeting (2014)

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