A series of mono-, di- and trimeric oxo-centred triruthenium cluster compounds with ortho-metallated polypyridyl ligands were prepared by reaction of oxo-centred triruthenium precursor compound [Ru3O(OAc)6(py)2(CH3OH)]+ (1) with bis(2,2′-bipyridin-5-yl)butadiyne (bpyCC–CCbpy), bis(2,2′-bipridin-5-yl)ethyne (bpyCCbpy), 2,2′-bipyrazine (bpz), pyrazino[2,3-f]quinoxaline (pyq), or 4,7-phenanthroline (4,7-phen). As revealed by redox wave splitting, electronic interactions are operating between two Ru3O redox centres in most of the triruthenium cluster dimers and trimers. The cluster–cluster interactions are highly sensitive to the variations in bonding modes of the polypyridyl ligands. Ortho-metallation of the bridging ligand induces an enhanced electronic interaction between two triruthenium centres.
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