Synthesis of [Ru-II(eta(6)-p-cymene)(PPh3)(L)Cl]PF6 complexes with carbohydrate-derived phosphites, imidazole or indazole co-ligands

Ru-II(arene) complexes of the general formula [Ru-II(eta(6)-p-cymene)(PPh3)(L)Cl]PF6 with L = P- or N-donor systems have been synthesized and characterized. Carbohydrate-derived phosphites, imidazole or indazole have been chosen as co-ligands and different synthetic routes have been explored to obtain the compounds. The organometallics were characterized by elemental analysis, electrospray ionization mass spectroscopy, H-1, C-13{H-1}, P-31{H-1} and 2D NMR spectroscopic methods. (C) 2011 Elsevier B.V. All rights reserved.

Binding of Organometallic Ruthenium(II) and Osmium(II) Complexes to an Oligonucleotide: A Combined Mass Spectrometric and Theoretical Study

Antoine Dorcier, Paul Joseph Dyson, Christian Gossens, Ursula Röthlisberger, Rosario Scopelliti, Ivano Tavernelli

Ru(II) and Os(II) p-cymene dichloride complexes with either a pta (1,3,5-triaza-7-phosphatricyclo[3.3.1.1]decane) or [pta-Me]Cl ligand which exhibit anticancer activity were prepd. and characterized by 1H and 31P NMR spectroscopy and mass spectrometry. Three of the complexes, viz. [Os(h6-p-cymene)Cl2(pta)] and [M(h6-p-cymene)Cl2(pta-Me)]Cl (M = Ru, Os), also were characterized by single-crystal x-ray diffraction. The pta complexes are selective anticancer agents, whereas the pta-Me+ complexes are indiscriminate and damage both cancer and healthy cells but represent models for the protonated pta adduct which was implicated in drug activity. To establish a link between their biol. activity and the effect they have on DNA (a likely in vivo target), the reactivity of the complexes toward a 14-mer oligonucleotide (5'-ATACATGGTACATA-3') was studied using electrospray ionization mass spectrometry. The complexes bind to the oligonucleotide with loss of chloride and in some cases loss of the arene. Loss of arene appears to be most facile with the Ru-pta complexes but also takes place with the Ru-pta-Me complexes, whereas arene loss is not obsd. for the Os complexes. As pH is reduced, increased binding to the oligonucleotide is obsd., as evidenced from mass spectrometric relative intensities. Binding energies between the metal centers and the surrounding ligands were calcd. using d. functional theory (DFT). The calcd. energies rationalize the exptl. obsd. tendencies for arene loss and show that the pta ligands are relatively strongly bound. Exchange of metal center (Ru vs. Os), methylation or protonation of the pta ligand, or change of the arene (p-cymene vs. benzene) results in significant differences in the metal-arene binding energies while leaving the metal-phosphine bond strength essentially unchanged. Significantly lower binding energies and reduced hapticity are predicted for the exchange of arene by nucleobases. The latter show higher binding energies for N s-bonding than for p-bonding. [on SciFinder (R)]

2005

Cytotoxicity of ruthenium-arene complexes containing B-ketoamine ligands

Catherine Marie Amélie Clavel, Paul Joseph Dyson, Rosario Scopelliti

New ruthenium(II) arene derivatives (arene = p-cymene, benzene, hexamethylbenzene) containing beta-ketoamine ligands L' (HL' in general; in detail, HLph,ph = (4Z)-3-methyl-4-((phenylamino)(phenyl)methylene)-1-phenyl-1H-pyrazol-5(4H)-one, HLnaph,ph = (4Z)-3-methyl-4-((phenyamino)(naphthalen-2-yl)methylene)-1-phenyl-1H-pyrazol-5(4H)- one, HLet,ph = (4Z)-3-methyl-4-(1-(phenylamino)propylidene)-1-phenyl-1Hpyrazol-5(4H)-one) have been synthesized and characterized by spectroscopy (IR, ESI-MS, H-1 and C-13 NMR) and elemental analysis. The ligands in the anionic form coordinate ruthenium in a chelating kappa N-2,O-bidentate fashion, affording 1:1 derivatives of the formula [Ru(arene)(L')Cl]. Further reaction of [Ru(p-cymene)(L')Cl] with AgPF6 or PTA (PTA = 1,3,5-triaza-7-phosphaadamantane) in methanol affords [Ru(p-cymene)(L')(CH3OH)] [PF6] and [Ru(p-cymene) (L')(PTA)]Cl, respectively. The solid-state structures of the ligand HLet,ph and complexes [Ru(p-cymene)(L-ph,L-ph)Cl] (1), [Ru(p-cymene)(L-naph,L-ph)Cl] (4), and [Ru(p-cymene)(L-et,L-ph)Cl] (7) have been determined by single-crystal X-ray diffraction. The antitumor activity of both the ligands and complexes has been evaluated against the human ovarian carcinoma cell line A2780 and its cisplatin-resistant equivalent A2780R, some of the complexes showing significant cytotoxicity toward the cisplatin-resistant cell line.

American Chemical Society2013

Syntheses, structures and properties of silver(I) complexes constructed from nitrogenous aromatic heterocyclic carboxylic acids and N-donor ligands

Chi Wai Cheung, Hong-Ling Gao

Four new coordination complexes with silver(I) ions and nitrogenous aromatic heterocyclic carboxylic ligands, namely [AB(4)(Pac)(Phen)(4)]center dot 8H(2)O (1), {[AB(4)(Pztc)(bPe)(3)] center dot 5H(2)O}(n) (2), [Ag-4(Hmptc)(2)(4,4'-bPY)(3)] center dot 4.5H(2)O (3), and [Ag-2(H(2)mPtc)(2)(2,2'-bPY)(2)] (4) (H(4)Pztc = pyrazine-2,3,5,6-tetracarboxylic acid, H(3)mptc = 6-methyl2,3,5-pyridine-tricarboxylic acid, phen = 1,10-phenanthroline, bpe = trans-1,2-bis(4-pyridyl)ethylene, 4,4'bpy = 4,4'-bipyridine, 2,2'-bpy = 2,2'-bipyridine), have been synthesized by the self-assembly reactions and characterized by X-ray diffraction single crystal structure analysis, elemental analysis, IR, PXRD, fluorescence and thermal analysis. In I, four crystallographically independent silver(l) atoms are found to coordinate with only one pztc(4-) ligand. Complex 2 is a 2D grid structure. Complexes 3 and 4 are extended from OD to 2D or 1D by the Ag center dot center dot center dot O interactions. (C) 2014 Elsevier B.V. All rights reserved.

Elsevier2014

Binding of Organometallic Ruthenium(II) and Osmium(II) Complexes to an Oligonucleotide: A Combined Mass Spectrometric and Theoretical Study

Antoine Dorcier, Paul Joseph Dyson, Christian Gossens, Ursula Röthlisberger, Rosario Scopelliti, Ivano Tavernelli

2005