540 Chemie und zugeordnete Wissenschaften
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- 1987 (1)
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- α-Iminoketones (1) (entfernen)
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Coordination of substitutionally inert [Ru(bpy)2]2+ fragments (bpy: 2,2′-bipyridine) to the a-iminoketone chelate ligands pyrazine-2-dimethylcarboxamide (4) and 4,7-phenanthroline-5,6-dione (5) yields the complexes [(N,O-4)Ru(bpy)2]2⊕, [(O,O′-5⊖)Ru(bpy)2]⊕ and {(N,O; N′,O′-5)[Ru(bpy)2]2}4⊕ which exhibit a rich electrochemistry. The distinctly different electronic structures of the complexes are evident from the ESR behaviour of paramagnetic intermediates: N.O-coordinated complexes have the unpaired electron residing in the ligand n system upon reduction, albeit with g<2 for the binuclear complex of 5. The paramagnetic O,O′-coordinated mononuclear complex with 5 has its redox potentials shifted positively relative to that of the binuclear system. These results are particularly noteworthy because 4 and 5 can be regarded as model compounds for the flavin and methoxatin dehydrogenase cofactors.