Dichlorido[1-(2-chloro­eth­yl)-3-(pyridin-4-ylmethyl-κN)urea](η6-hexa­methyl­benzene)­ruthenium(II) chloro­form monosolvate

The RuII atom in the title compound, [RuCl2(C12H18)(C9H12ClN3O)]·CHCl3, exhibits a typical piano-stool coordination, defined by a hexa­methyl­benzene ligand, two chloride ligands and a pyridyl­urea ligand coordinated through the pyridine N atom. In the crystal, a dimeric structure is observed due to two strong N—H⋯Cl inter­actions between the NH groups of urea and the two chloride ligands of neighbouring mol­ecules. In addition, the C=O group of the urea moiety inter­acts with the solvent mol­ecule through weak C—H⋯O interactions

Inducing Helical Chirality by Deforming Hexanuclear Metalloprismatic Structures

A comparative structural study of eleven empty and eight filled hexanuclear metalloprismatic cages reveals helical chirality depending on the twist angle between the upper and lower triangles defined by three metal centres

(η6-p-Cymene)bis­(trichlorido­stannyl)(triethoxy­phosphine-κP)ruthenium(II)

In the title complex, [RuSn2(C10H14)Cl6(C6H15O3P)], the Ru—Sn bond lengths [2.5619 (3) and 2.5669 (3) Å] are about 0.3 Å shorter than the sum of the covalent Ru and Sn radii (1.46 + 1.39 = 2.85 Å), in line with other structurally characterized arene ruthenium trichlorido­stannyl derivatives. The Ru(II) atom is surrounded by a para-cymene, a triethylphosphite and two trichloridostannyl ligands in a typical piano-stool coordination

Interaction of a ruthenium hexacationic prism with amino acids and biological ligands: ESI mass spectrometry and NMR characterisation of the reaction products

Reactions between the cationic triangular metallaprism [(p-cymene)6Ru6(tpt)2(dhnq)3]6+ ([1]6+) [tptis2,4,6-tri(pyridine-4-yl)-1,3,5-triazine; dhnqis5,8-dihydroxy-1,4-naphthoquinonato] and Arg, His, Lys, ascorbic acid, lactic acid and glutathione (GSH) have been studied at 37°C in aqueous solution at pD 7 using NMR spectroscopy and electrospray ionisation mass spectrometry. Coordination to the imidazole nitrogen atom of His or to the basic NH/NH2 groups in Arg and Lys slowly displaces the dhnq and tpt ligands from the (p-cymene)Ru units, and subsequently additional coordination to the amino and carboxylato groups forms stable N,N,O metallacycles. Compared with our previously reported study with the analogous metallaprism [(p-cymene)6Ru6(tpt)2(dhbq)3]6+ ([2]6+) (dhbqis2,5-dihydroxy-1,4-benzoquinonato), the larger metallaprism [1]6+ appears to be significantly more stable, and disassembled in the presence of Arg, His and Lys after only 12h of incubation. Moreover, the reaction with His is not complete, since only 14% of His reacted after more than 1week of incubation. Solutions of [1]6+ are also able to catalyse oxidation of the thiol group of Cys and GSH to give the corresponding disulfides and of ascorbic acid to give the corresponding dehydroascorbic acid. However, the results are markedly different from those obtained with metallaprism [2]6+: the oxidation of Cys and ascorbic acid is not complete, and the formation of intermediate adducts could be evidenced. On the other hand, the oxidation of GSH remains fast and is completed after only 12h. Oxidation of GSH to give the corresponding disulfide may explain its higher in vitro anticancer activity as compared with [2]6+. Our results suggest that metallaprism [1]6+ is more robust than [2]6+, may remain intact in the bloodstream and, therefore, may enter cancer cells undamaged, thus confirming the drug delivery potential for such water-soluble organometallic cage

Dichlorido(furfuryl­amine-κN)(η6-hexa­methyl­benzene)­ruthenium(II)

The single-crystal X-ray structure analysis of [RuCl2(C12H18)(C5H7NO)] reveals a distorted piano-stool geometry around the RuII atom, with a hexa­methyl­benzene ligand, two chloride ligands and a furfuryl­amine ligand, the latter coordinating through the amine group. In the crystal, a dimeric structure is observed as a result of N—H⋯Cl inter­actions between two symmetry-related mol­ecules

The Role of the Second Coordination Sphere in the Biological Activity of Arene Ruthenium Metalla-Assemblies

For nearly 15 years, the biological and biomedical applications of arene ruthenium metalla-assemblies have flourished. Today, the synthetic strategies to generate arene ruthenium assemblies are well-established, and these compounds offer tremendous possibilities in terms of structural diversities and chemical properties. However, the second coordination sphere is often poorly considered, if not ignored, when designing such arene ruthenium metalla-assemblies. These weak interactions (hydrogen bonding, hydrophobic, ionic, electrostatic, van der Waals, π-π stacking) that take place in the solid state or in solution are generally key interactions for the foreseen applications. Therefore, in this review, we want to emphasize this important property of arene ruthenium metalla-assemblies by showing examples dealing with second coordination sphere interactions and how this can be better integrated in the design of these versatile supramolecular metal-based entities