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Mono- and binuclear bis(2,2'-bipyridine)ruthenium complexes with N,O-ligands modeling dehydrogenase cofactors

, , , and . Zeitschrift fuer Naturforschung, B: A Journal of Chemical Sciences, 42 (4): 425--430 (1987)
DOI: 10.1515/znb-1987-0407

Abstract

Coordination of substitutionally inert Ru(bpy)22+ fragments (bpy = 2,2'-bipyridine) to the a-iminoketone chelate ligands pyrazine-2-dimethylcarboxamide (L) and 4,7-phenanthroline-5,6-dione (HL') yields Ru(bpy)2(L-N,O)2+, Ru(bpy)2(L'-O,O')+, and ((L'-N,O;N',O')Ru(bpy)224+ which exhibit a rich electrochem. The distinctly different electronic structures of the complexes are evident from the ESR behavior of paramagnetic intermediates: N,O-coordinated complexes have the unpaired electron residing in the ligand p system upon redn., albeit with g \textless2 for the complex of L but with g \textgreater2 for the binuclear complex of HL'. The paramagnetic O,O'-coordinated mononuclear complex with (L') has its redox potentials shifted pos. relative to that of the binuclear system. These results are particularly noteworthy because L and HL' can be regarded as model compds. for the flavin and methoxatin dehydrogenase cofactors. on SciFinder(R)

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