Abstract:In the title compound, [RuCl2(C10H8N2)2], the Ru atom is located on a crystallographic inversion center. The bipyridine (bpy) ligands are thus coordinated trans, leading to steric interactions between pairs of opposite ortho‐H atoms. The result is a marked deviation from the expected planarity of some units; the two pyridine rings of an individual bpy ligand enclose a 23.8 (1)° angle. With the RuN4 plane, the same pyridine rings enclose angles of 22.3 (1) and 21.0 (1)°. The octahedral environment of the Ru ato… Show more
Most studies of ruthenium polypyridine complexes are devoted to their cis isomers. The fact that cis isomers are thermally more stable and thus easier to synthesize has prevented researchers from investigating the properties and applications of trans complexes. We present a study of thermal and photochemical cis−trans interconversion of the key complex [Ru-(bpy) 2 (PMe 3 )(H 2 O)] 2+ (bpy = 2,2′-bipyridine, PMe 3 = trimethylphosphine), which results in specific synthetic applications of the trans species, potentially useful as a platform for designing highly efficient visible light activated caged compounds. We show, as a proof of concept, some examples of trans complexes bearing N-donor and P-donor ligands and their comparison with the cis isomers.
Most studies of ruthenium polypyridine complexes are devoted to their cis isomers. The fact that cis isomers are thermally more stable and thus easier to synthesize has prevented researchers from investigating the properties and applications of trans complexes. We present a study of thermal and photochemical cis−trans interconversion of the key complex [Ru-(bpy) 2 (PMe 3 )(H 2 O)] 2+ (bpy = 2,2′-bipyridine, PMe 3 = trimethylphosphine), which results in specific synthetic applications of the trans species, potentially useful as a platform for designing highly efficient visible light activated caged compounds. We show, as a proof of concept, some examples of trans complexes bearing N-donor and P-donor ligands and their comparison with the cis isomers.
The title compound, trans-[Ru(bpy)2(H2O)2](CF3SO3)2 (bpy = 2,2′-bipyridine, C10H8N2), crystallized from the decomposition of an aged aqueous solution of a dimeric complex of cis-Ru(bpy)2 in 0.1 M triflic acid. The RuII ion is located on a crystallographic inversion center and exhibits a distorted octahedral coordination with equivalent ligands trans to each other. The Ru—O distance is 2.1053 (16) Å and the Ru—N distances are 2.0727 (17) and 2.0739 (17) Å. The bpy ligands are bent, due to inter-ligand steric interactions between H atoms of opposite pyridyl units across the Ru center. The crystal structure exhibits an extensive hydrogen-bonding network involving the water ligands and the trifluoromethanesulfonate counter-ions within two-dimensional layers, although no close hydrogen-bond interactions exist between different layers.
In the crystal structure of the ruthenium(III) complex, trans-[RuIII(dcbpy)2Cl2]ClO4 (dcbpy = 2,2′-bipyridine-4,4′-dicarboxylic acid, C12H8N2O4), the RuIII atom lies on an inversion centre, showing a small distortion in its octahedral environment. The Ru—Cl bond lengths are shorter than those present in the analogous trans-ruthenium(II) compound containing the bipyridine ligand. The C—O distances in the two symmetry-independent carboxylic acid moieties of the ligand are similar in one group, but different in the other. This is probably due to the different intermolecular interactions they experience with neighbouring cationic complexes. The hydrogen-bonding interactions in which they are involved form a three-dimensional structure, similar to those found in coordination polymers.
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