A New Family of Mono- and Dicarboxylic Ruthenium Complexes [Ru(DIP)<sub>2</sub>(L<sub>2</sub>)]<sup>2+</sup> (DIP = 4,7-diphenyl-1,10-phenanthroline): Synthesis, Solution Behavior, and X-ray Molecular Structure of <i>trans</i>-[Ru(DIP)<sub>2</sub>(MeOH)<sub>2</sub>][OTf]<sub>2</sub>
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A new family of ruthenium complexes of general formula [Ru(DIP)2(L2)]2+, where DIP = 4,7-diphenyl-1,10-phenanthroline, a bidentate ligand with an extended aromatic system, was prepared and fully characterized. When L is a monodentate ligand, the following complexes were obtained: L = CF3SO3-1 (2), CH3CN (3), and MeOH (4). When L2 is a bidentate ligand, the compounds [Ru(DIP)2(Hcmbpy)][Cl]2 (5) and [Ru(DIP)2(H2dcbpy)][Cl]2 (6) were prepared (Hcmbpy = 4-carboxy-4‘-methyl-2,2-bipyridine, H2dcbpy = 4,4‘-dicarboxy-2,2‘-bipyridine). Complex [Ru(DIP)2(MeOH)2][OTf]2 (4) displayed a trans configuration of the DIP ligands, which is rare for octahedral complexes featuring DIP bidentate ligands. DFT calculations carried out on 4 showed that the cis isomer is more stable by 12.2 kcal/mol relative to the trans species. The solution behaviors of monocarboxylic complex [Ru(DIP)2(Hcmbpy)][Cl]2 (5) and dicarboxylic complex [Ru(DIP)2(H2dcbpy)][Cl]2 (6) were investigated by 1H NMR spectroscopy. VT-NMR, concentration dependence, and reaction with NaOD allowed us to suggest that aggregation of the cationic species in solution, especially for 6, originates mainly from hydrogen bonding interactions.
