Hydrogen bonding in diruthenium(II,III) tetraacetate complexes with biologically relevant axial ligands |
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| Authors: | Brendan R.A. Bland George Vamvounis T. Stanley Cameron |
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| Affiliation: | a Department of Chemistry, St. Francis Xavier University, P.O. Box 5000, Antigonish, NS, Canada B2G 2W5
b Department of Chemistry, Dalhousie University, Halifax, NS, Canada B3H 4J3 |
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| Abstract: | Three diadduct complexes of the mixed-valent form of diruthenium tetraacetate, [Ru2(μ-O2CCH3)4L2](PF6), where L are the biologically relevant ligands imidazole, 1, 7-azaindole, 2, and caffeine, 3, were synthesized and characterized by elemental analysis, IR and UV-Vis spectroscopy and X-ray crystallography. In order to further elucidate the potential interactions of these dimers with DNA, the nature of the ligand coordination and the secondary inter- and intramolecular hydrogen-bonding interactions in all three complexes were assessed. Complex 1 · CH2Cl2 shows, exclusively, intermolecular interactions with the  counterion whereas complexes 2 · ClCH2CH2Cl and 3 · OC(CH3)2 · H2O, in addition to extensive intermolecular interactions, show intramolecular hydrogen bonding from the axial ligand to the bridging acetate oxygens, locking the ligand mean planes in place between the bridging acetate mean planes. In addition, all three complexes display π-π stacking of axial ligand rings on adjacent diadduct units. |
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| Keywords: | Diruthenium tetracarboxylates X-ray crystal structures Hydrogen bonding π-π stacking |
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