Résultat de la recherche
The Complex-in-a-Complex Cations [(acac)2M⊂Ru6(p-iPrC6H4Me)6(tpt)2 (dhbq)3]6+: A Trojan Horse for Cancer Cells
Remarkable Anticancer Activity of Triruthenium-Arene Clusters Compared to Tetraruthenium-Arene Clusters
The in vitro activity of a series of ruthenium clusters, [(η6-C6H6)(η6-C6Me6)2Ru3 (μ-H)3 (μ3-O)][BF4], [(η6-C6H6)(η6-1,4-iPrC6H4Me)(η6-C6Me6)Ru3 (μ-H)3 (μ3-O)][BF4], [(η6-C6H6)4Ru4 (μ-H)4][BF4]2, [(η6-C6H5Me)4Ru4 (μ-H)4][BF4]2 and [(η6-C6H6)4Ru4 (μ-H)3 (μ-OH)][Cl]2, has been evaluated against A2780 and A2780cisR ovarian carcinoma cell lines. Both triruthenium clusters are very active compared to ruthenium compounds in general, whereas the tetraruthenium clusters do not display significant cytotoxicities. Since the triruthenium clusters are known to form supramolecular interactions with arenes and other functions, it is possible that such interactions are also important with respect to their mode of biological activity. The X-ray structure analysis of [(η6-C6H5Me)4Ru4 (μ-H)4][PF6]2 is also reported.
Dinuclear ruthenium sawhorse-type complexes containing carboxylato bridges and ferrocenyl substituents: Synthesis and electrochemistry
The ferrocenyl-containing diruthenium complexes [Ru2(CO)4(μ2-η2-OOCFc)2L2] (Fc = ferrocenyl, fc = ferrocen-1,1′-diyl; 1: L = NC5H4–COOC6H4–OC10H21, 2: L = NC5H4–COOC6H4–OC16H33, 3: L = NC5H4–OOC–fc–C12H25) and [Ru2(CO)4(μ2-η2-OOC6H5)2(NC5H4–OOC–fc–C12H25)2] (4) have been synthesized from Ru3(CO)12, ferrocene carboxylic or benzoic acid and the corresponding pyridine derivative. The synthesis of the new pyridine derivative NC5H4–OOC–fc–C12H25 used for the preparation of 3 and 4 is also reported. Complexes 1–4 posses a so-called sawhorse structure consisting of the Ru2(CO)4 backbone and two bridging carboxylato ligands, while the coordination sphere around the ruthenium atoms is completed by the pyridine-derived ligands bonded in the axial positions. The electrochemical behavior of 1–4 and their known analogues [Ru2(CO)4(μ2-η2-OOCFc)2L2] (5: L = NC5H5, 6: L = P(C6H5)3, 7: L = NC5H4–OOCFc) has been studied by voltammetry on rotating disc electrode and by cyclic voltammetry.
Synthesis and molecular structure of trinuclear mixed-metal cluster cations containing arene and hydrido ligands
The mixed-metal trinuclear cluster cations [H3Ru2(C6Me6)2Os(C6H6)(O)]+ (1), [H3Ru2 (1,2,4,5-C6H2Me4)2Os(p-MeC6H4iPr)(O)]+ (2) and [H3Ru2 (1,2,4,5-C6H2Me4)2Os(C6H6)(O)]+ (3) have been synthesised from the corresponding dinuclear precursors [H3Ru2(arene)2]+ and the corresponding mononuclear complexes [Os(arene)(H2O) 3]2+, isolated and characterised as the tetrafluoroborate and hexafluorophosphate salts. The cations 1, 2 and 3 are heteronuclear analogues of the cluster cation [H3Ru3(C6H6)(C6Me6)2 (O)]+ that possesses a homonuclear metallic core. The single-crystal X-ray structure analyses of [1][BF4], [2][PF6] and [3][PF6] reveal an equiangular metal triangle despite the presence of an osmium atom in the metallic core.
Organometallic boxes built from 5,10,15,20-tetra(4-pyridyl)porphyrin panels and hydroxyquinonato-bridged diruthenium clips
Self-assembly of 5,10,15,20-tetra(4-pyridyl)porphyrin (tpp-H2) tetradentate panels with dinuclear arene ruthenium clips [Ru2 (η6-arene)2 (dhbq)Cl2] (arene = C6H5Me, p-PriC6H4Me, C6Me6; dhbq = 2,5-dihydroxy-1,4-benzoquinonato) affords the cationic organometallic boxes [Ru8 (η6-C6H5Me)8 (tpp-H2)2 (dhbq)4]8+ ([1]8+), [Ru8 (η6-p-PriC6H4Me)8 (tpp-H2)2(dhbq)4]8+ ([2]8+) and [Ru8 (η6-C6Me6)8 (tpp-H2)2 (dhbq)4]8+ ([3]8+). These octanuclear cations have been isolated as their triflate salts and characterised by mass spectrometry, NMR and IR spectroscopy. The molecular structure of these systems was deduced by one-dimensional and two-dimensional NMR experiments (ROESY, COSY, HSQC).
Mono and dinuclear arene ruthenium complexes containing 6,7-dimethyl-2,3-di(pyridine-2-yl)quinoxaline as chelating ligand: Synthesis and molecular structure
The mononuclear cations of the general formula [(η6-arene)RuCl(dpqMe2)]+ (dpqMe2 = 6,7-dimethyl-2,3-di(pyridine-2-yl)quinoxaline; arene = C6H6, 1; C6H5Me, 2; p-PriC6H4Me, 3; C6Me6, 4) as well as the dinuclear dications [(η6-arene) 2Ru2Cl2(μ-dpqMe2)]2+ (arene = C6H6, 5; C6H5Me, 6; p-PriC6H4Me, 7; C6Me6, 8) have been synthesised from 6,7-dimethyl-2,3-di(pyridine-2-yl)quinoxaline (dpqMe2) and the corresponding chloro complexes [(η6-C6H6)Ru(μ-Cl)Cl]2, [(η6-C6H5Me)Ru(μ-Cl)Cl]2, [(η6-p-PriC6H4Me)Ru(μ-Cl)Cl]2 and [(η6-C6Me6)Ru(μ-Cl)Cl]2, respectively. The X-ray crystal structure analyses of [1][PF6], [3][PF6] and [6][PF6]2 reveal a typical piano-stool geometry around the metal centre; in the dinuclear complexes the two chloro ligands, with respect to each other, are found to be trans oriented.
New mono and dinuclear arene ruthenium chloro complexes containing ester substituents
The dinuclear arene ruthenium complexes [RuCl2{C6H5(CH2)3OCO-p-C6H4-OC8H17}]2 (1) and [RuCl2{p-C6H4(CH2COOCH2CH3)2}]2 (2) have been obtained by dehydrogenation of the corresponding cyclohexadiene derivative with ruthenium chloride hydrate. The single-crystal X-ray structure analysis of 2 shows the arene ligands to be involved in slipped-parallel π–π stacking interactions with neighbouring molecules, thus forming infinite chains along the b-axis. The dinuclear complexes 1 and 2 react with two equivalents of triphenylphosphine (PPh3) to give in excellent yield the corresponding mononuclear phosphine complexes [RuCl2{C6H5(CH2)3OCO-p-C6H4-OC8H17}(PPh3)] (3) and [RuCl2{p-C6H4(CH2COOCH2CH3)2}(PPh3)] (4), respectively. The single-crystal X-ray structure analysis of 4 reveals the formation of a dimer through two C–HCl interactions in the solid state.
Mononuclear arene ruthenium complexes containing 5,6-diphenyl-3-(pyridine-2-yl)-1,2,4-triazine as chelating ligand: Synthesis and molecular structure
The mononuclear cations of the general formula [(η6-arene)RuCl(pdpt)]+ (pdpt = 5,6-diphenyl-3-(pyridine-2-yl)-1,2,4-triazine; arene = C6H6 (1); C6H5Me (2); p-PriC6H4Me (3); C6Me6 (4)) have been synthesised from 5,6-diphenyl-3-(pyridine-2-yl)-1,2,4-triazine (pdpt) and the corresponding chloro complexes [(η6-C6H6)Ru(μ-Cl)Cl] 2, [(η6-C6H5Me)Ru(μ-Cl)Cl]2, [(η6p-PriC6H4Me)Ru(μ-Cl)Cl]2 and [(η6-C6Me6)Ru(μ-Cl)Cl]2, respectively. The X-ray crystal structure analyses of [1][PF6] • (C6H6)2.5 and [2][PF6] • (CH3CN)2 reveal a typical piano-stool geometry around the metal centre and in the crystal packing a complexed networks of intermolecular interactions.
Ru2(CO)4(OOCR)2(PPh3)2 sawhorse-type complexes containing μ2-η2-carboxylato ligands derived from biologically active acids
The thermal reaction of Ru3(CO)12 with the biologically active acids acetyl salicylic acid (Aspirin), α-methyl-4-(isobutyl)phenylacetic acid (Ibuprofen) and 3α,7α,12α-trihydroxy-5β-cholanic acid (cholic acid) in refluxing tetrahydrofuran, followed by addition of triphenylphosphine, gives the dinuclear complexes Ru2 (CO) 4(OOCR)2(PPh3)2 (1: R = C6H4-2-OCOMe, 2: R = CHMe-C6H4-4-Bui, 3: C23H39O3). The single-crystal structural analysis of 1 and 2 reveals a dinuclear Ru2(CO)4 sawhorse structure, the diruthenium backbone being bridged by the carboxylato ligands, while the two phosphine ligands occupy the axial positions at the ruthenium atoms. However, chiral carbon atoms in the carboxylic acid undergo racemisation during the thermal reaction.