74006-30-7Relevant academic research and scientific papers
Coordination of 9-ethylguanine to the mixed-ligand compound α-[Ru(azpy)(bpy)Cl2 (azpy = 2-phenylazopyridine and bpy = 2,2′-bipyridine). An unprecedented ligand positional shift, correlated to the cytotoxicity of this type of [RuL2Cl2] (with L = azpy or bpy) complex
Hotze, Anna C. G.,Van Der Geer, Erwin P. L.,Caspers, Sabrine E.,Kooijman, Huub,Spek, Anthony L.,Haasnoot, Jaap G.,Reedijk, Jan
, p. 4935 - 4943 (2004)
The striking difference in cytotoxic activity between the inactive cis-[Ru(bpy)2Cl2 and the recently reported highly cytotoxic α-[Ru(azpy)2Cl2 (α indicating the isomer in which the coordinating Cl atoms, pyridine nitrogens, and azo nitrogens are in mutual cis, trans, cis orientation) encouraged the synthesis of the mixed-ligand compound cis-[Ru(azpy)(bpy)Cl2]. The synthesis and characterization of the only occurring isomer, i.e., α-[Ru(azpy)(bpy) Cl2], 1 α denoting the isomer in which the Cl ligands are cis related to each other and the pyridine ring of azpy is trans to the pyridine ring of bpy), are described. The solid-state structure of 1 has been determined by X-ray structure analysis. The IC50 values obtained for several human tumor cell lines have indicated that compound 1 shows mostly a low to moderate cytotoxicity. The binding of the DNA model base 9-ethylguanine (9-EtGua) to the hydrolyzed species of 1 has been studied and compared to DNA model base binding studies of cis-[Ru(bpy)2Cl2] and α-[Ru(azpy)2Cl2]. The completely hydrolyzed species of 1, i.e., α-[Ru(azpy)(bpy)(H2O)2]2+, has been reacted with 9-EtGua in water at room temperature for 24 h. This resulted in the monofunctional binding of only one 9-EtGua, coordinated via the N7 atom. The product has been isolated as α-[Ru(azpy)(bpy)(9-EtGua)(H 2O)](PF6)2, 2, and characterized by 2D NOESY NMR spectroscopy. The NOE data show that the 9-EtGua coordinates (under these conditions) at the position trans to the azo nitrogen atom. Surprisingly, time-dependent 1H NMR data of the 9-EtGua adduct 2 in acetone-d 6 show an unprecedented positional shift of the 9-EtGua from the position trans to the azo nitrogen to the position trans to the bpy nitrogen atom, resulting in the adduct α′-[Ru(azpy)(bpy)(9-EtGua)(H 2O)]-(PF6)2 (α′ indicating 9-EtGua is trans to the bpy nitrogen). This positional isomerization of 9-EtGua is correlated to the cytotoxicity of 1 in comparison to both the cytotoxicity and 9-EtGua coordination of cis-[Ru(bpy)2Cl2], α-[Ru(azpy)2Cl2], and β-[Ru(azpy) 2Cl2]. This positional isomerization process is unprecedented in model base metal chemistry and could be of considerable biological significance.
Attachment of a RuII Complex to a Self-Folding Hexaamide Deep Cavitand
Korom, Sa?a,Ballester, Pablo
supporting information, p. 12109 - 12112 (2017/09/12)
We report the design, synthesis and characterization of a new RuII metallocavitand that is catalytically active in alkene epoxidation reactions. The elaboration of the resorcin[4]arene's aromatic cavity produced a self-folding, deep hexaamide cavitand featuring a single diverging terpyridine (tpy) group installed at its upper rim. The construction of the metallocavitand involved the initial chelation of a RuIII chloride complex by the tpy ligand followed by the incorporation of 2-(phenylazo)pyridine (azpy) as an ancillary ligand. The resulting RuII chloro complex was converted into the catalytically active aqua counterpart by a ligand exchange process.
Dichlorobis(2-phenylazopyridine)ruthenium(II) complexes: characterisation, spectroscopic and structural properties of four isomers.
Velders, Aldrik H,van der Schilden, Karlijn,Hotze, Anna C G,Reedijk, Jan,Kooijman, Huub,Spek, Anthony L
, p. 448 - 455 (2007/10/03)
The didentate ligand 2-phenylazopyridine (azpy) can--in theory--give rise to five different isomeric complexes of the type [Ru(azpy)2Cl2], of which three have been known since 1980. The molecular structures of the cis-dichlorobis(2-phenylazopyridine) ruthenium(II) complexes alpha-[Ru(azpy)2Cl2] and beta-[Ru(azpy)2Cl2](in which the coordinating pyridine nitrogen atoms are in mutually trans and cis positions, respectively, whilst the azo nitrogen atoms are in mutually cis positions) were unambiguously determined in the early 1980s. The third isomer, gamma-[Ru(azpy)2Cl2], has for two decades, erroneously, been assumed to be the all-trans isomer. In a recent communication we have proven that for this gamma isomer the chloride ions are indeed in a trans geometry, but the pyridine nitrogen and azo nitrogen atoms of the two azpy ligands are in mutually cis geometries. In this paper the isolation of a fourth isomer is presented, the hitherto unknown delta-[Ru(azpy)2Cl2]. The isomeric structure of delta-[Ru(azpy)2Cl2] has been determined by 1H-NMR spectroscopy and single-crystal X-ray diffraction analysis, and is the all-trans isomer. The bis(azpy)-ruthenium(II) isomers are of interest because of the pronounced cytotoxicity they exhibit against tumour cell lines and could be very useful in the search for structure-activity relationships of antitumour-active ruthenium complexes, as among the isomers there is a significant difference in activity. It is of paramount importance to have a good understanding of the structural and spectroscopic properties of these complexes, which in this paper are compared and discussed, with a particular emphasis on 1D and 2D 1H NMR spectroscopies. Copyright 2004 The Royal Society of Chemistry
Use of Silver(I) Complexes in Synthesis of Bis- and Tris- Complexes of Ruthenium(II) and Investigation of Solid-state Isomerisation
Deb, Alok K.,Kakoti, Maushumi,Goswami, Sreebrata
, p. 3249 - 3252 (2007/10/02)
Efficient, new and direct synthetic routes to isomeric and 2*H2O complexes, based on the reaction of hydrated RuCl3 and ClO4, have been elaborated.The identity of the compounds were established from el
