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1.
The reaction of [C5H4(CH2)nX]Tl (1: n = 2, X = NMe2, OMe, CN; n = 3, X = NMe2) with [(η6-C6H6)RuCl(μ-Cl)]2, 2, afforded the sandwich compounds [{η5-C5H4(CH2)nX}Ru(η6-C6H6)]PF6, 3, and [η5-C5H4(CH2)nX]2Ru, 4. Photolytic cleavage of 3 in acetonitrile afforded the tethered products [{η5:κN-C5H4(CH2)nX}Ru(CH3CN)2]PF6, 5. 相似文献
2.
Moreno V Font-Bardia M Calvet T Lorenzo J Avilés FX Garcia MH Morais TS Valente A Robalo MP 《Journal of inorganic biochemistry》2011,105(2):241-249
Four ruthenium(II) complexes with the formula [Ru(η5-C5H5)(PP)L][CF3SO3], being (PP = two triphenylphosphine molecules), L = 1-benzylimidazole, ; (PP = two triphenylphosphine molecules), L = 2,2′bipyridine, ; (PP = two triphenylphosphine molecules), L = 4-Methylpyridine, ; (PP = 1,2-bis(diphenylphosphine)ethane), L = 4-Methylpyridine, , were prepared, in view to evaluate their potentialities as antitumor agents. The compounds were completely characterized by NMR spectroscopy and their crystal and molecular structures were determined by X-ray diffraction. Electrochemical studies were carried out giving for all the compounds quasi-reversible processes. The images obtained by atomic force microscopy (AFM) suggest interaction with pBR322 plasmid DNA. Measurements of the viscosity of solutions of free DNA and DNA incubated with different concentrations of the compounds confirmed this interaction. The cytotoxicity of compounds 1234 was much higher than that of cisplatin against human leukemia cancer cells (HL-60 cells). IC50 values for all the compounds are in the range of submicromolar amounts. Apoptotic death percentage was also studied resulting similar than that of cisplatin. 相似文献
3.
Three binuclear ruthenium complexes with dendritic side chains, 1,4-[RuCl(CO)(PMe3)3CHCH]2C6H2-2,5-(Gn)2 with Gn = G0 (1), G1 (2), and G2 (3), have been synthesized by the reactions of the corresponding diethynylaryls with the ruthenium hydride complex [RuHCl(CO)(PPh3)3] and subsequent ligand exchange with PMe3. The complexes have been characterized by elemental analysis, NMR, and UV-Vis spectrophotometry. The structure of complex 1 has been determined by X-ray crystallography. Their electrochemical properties have been investigated. Electrochemical studies in solution may imply that the two metal centers in complexes 1-3 have good electronic communications between each other. However, the electron communication is not effectively enhanced with increasing generation of the dendrons in solution. 相似文献
4.
Treatment of [(η6-p-cymene)RuCl(μ-Cl)]2 with Lawesson’s reagent [ArP(S)(μ-S)]2 (Ar = p-C6H4OMe) in the presence of ammonium hydroxide afforded the dinuclear complex [(η6-p-cymene)Ru{μ-η1(S),η2(S,S′)-ArP(O)S2}]2 (1) in which the tripodal [ArP(O)S2]2− ligands bind to the ruthenium atom in both bridging and chelating modes with two non-coordinating PO groups. Interaction of [RuHCl(CO)(PPh3)3] with [ArP(S)(μ-S)]2 and bis(diphenylphosphino)methane (dppm) in the presence of ammonium hydroxide gave the dinuclear complex [Ru(CO){μ3-η1(O),η2(S,S′)-ArP(O)S2}(dppm)]2 (2) in which the tripodal [ArPOS2]2− ligands bind the two Ru atoms via both sulfur and oxygen atoms. Treatment of [Ru(PPh3)3Cl2] with [ArP(S)(μ-S)]2 at reflux in the presence of ammonium hydroxide led to the formation of the dinuclear mixed valence complex [Ru2Cl2(μ-S){μ3-η1(O),η1(S),-η2(S,S′)-ArP(O)S2}(PPh3)3] (3), which contains a [RuII(PPh3)2Cl]+ and [RuIV(PPh3)Cl]3+ moieties by the tripodal [ArPOS2]2− ligand in a μ3-η1(O),η1(S),η2(S,S′) coordination mode and the μ-S2− anion. The crystal structures of 1, 2, and 3·CH2Cl2 along with their spectroscopic and electrochemical properties are reported. 相似文献
5.
Wai-Man Cheung 《Inorganica chimica acta》2006,359(3):782-788
Treatment of [Cp*RuCl2]x (Cp* = η5-C5Me5) with K[N(Ph2PS)2] afforded [Cp*Ru{N(Ph2PS)2}Cl] (1). Reduction of 1 with Li[BEt3H] gave the 16-electron half-sandwich Ru(II) complex [Cp*Ru{N(Ph2PS)2}] (2). Complexes 1 and 2 have been characterized by X-ray crystallography. The Ru-Cp*(centroid) and average Ru-S distances in 1 are 1.827 and 2.3833(5) Å, respectively. The corresponding bond distances in 2 are 1.739 and 2.379(1) Å. Treatment of 2 with 2-electron ligands L afforded the adducts [Cp*Ru{N(Ph2PS)2}L] (L = CO (3), 2,6-Me2C6H4NC (4), MeCO2CCCO2Me (5)). Oxidation of 2 with tetramethylthiuram disulfide gave the Ru(IV) complex [Cp*Ru{S2CNMe2}2][N(Ph2PS)2] (6). The Ru-Cp*(centroid) and average Ru-S distances in 6 are 1.897 and 2.387(1) Å, respectively. 相似文献
6.
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. 相似文献
7.
Jennifer C. Gray Abraha Habtemariam Marcel Winnig Wolfgang Meyerhof Peter J. Sadler 《Journal of biological inorganic chemistry》2008,13(7):1111-1120
The novel organometallic sandwich complexes [(eta(6)-p-cymene)Ru(eta(6)-aspartame)](OTf)(2) (1) (OTf = trifluoromethanesulfonate) and [(eta(6)-p-cymene)Os(eta(6)-aspartame)](OTf)(2) (2) incorporating the artificial sweetener aspartame have been synthesised and characterised. A number of properties of aspartame were found to be altered on binding to either metal. The pK (a) values of both the carboxyl and the amino groups of aspartame are lowered by between 0.35 and 0.57 pH units, causing partial deprotonation of the amino group at pH 7.4 (physiological pH). The rate of degradation of aspartame to 3,6-dioxo-5-phenylmethylpiperazine acetic acid (diketopiperazine) increased over threefold from 0.12 to 0.36 h(-1) for 1, and to 0.43 h(-1) for 2. Furthermore, the reduction potential of the ligand shifted from -1.133 to -0.619 V for 2. For the ruthenium complex 1 the process occurred in two steps, the first (at -0.38 V) within a biologically accessible range. This facilitates reactions with biological reductants such as ascorbate. Binding to and activation of the sweet taste receptor was not observed for these metal complexes up to concentrations of 1 mM. The factors which affect the ability of metal-bound aspartame to interact with the receptor site are discussed. 相似文献
8.
Tarun K. Panda 《Inorganica chimica acta》2008,361(8):2236-2242
The Lewis acid-base reaction of 2,6-bis[1,3-di-tert-butylimidazolin-2-imino)methyl]pyridine (TLtBu) and LnCl3 in THF leads to the corresponding neutral lanthanide complexes of type [(TLtBu)LnCl3], Ln = Y (1a), Er (1b), Lu (1c). The yttrium and lutetium complexes have been characterized by X-ray diffraction analysis. The solid state structures reveal that the bulky TLtBu ligand causes steric crowding around the lanthanide atoms by coordinating to the metal center in a tridentate fashion. In addition, remote C-H?Ln interactions (H?Ln ca. 2.7 Å) involving one of the tBu methyl groups are observed in both cases. A DFT (density functional theory) calculation on 1a was able to reproduce this interaction, which was additionally characterized by means of an H?Y compliance constant and by employing the AIM (atoms in molecules) theory. 相似文献
9.
A series of ruthenium and rhodium complexes with a urea-disubstituted pyridine ligand are reported. The X-ray crystal structures of three of these species, RuCl2(L1)(PPh3) (1), [Ru(MeCN)2(L1)(PPh3)][BF4]2 (3) and Rh(CH2Cl)Cl2(L1) (9) (where L1 = N,N′-(2,2′-(1E,1′E)-(1,1′-(pyridine-2,6-diyl)bis(ethan-1-yl-1-ylidene))bis(azan-1-yl-1-ylidene)bis(ethane-2,1-diyl))diacetamide) have shown that the disubstituted pyridine acts as a tridentate ligand and its urea substituents engage in hydrogen bonding interactions with species coordinated to the metal centres. The reactivity of the ruthenium complexes towards coordination of other anions such as NCS− has been investigated, as well as the oxidative-addition of alkyl chlorides to rhodium(I) centres (to yield species such as 9). 相似文献
10.
Craig Streu Patrick J. Carroll Ronen Marmorstein Eric Meggers 《Inorganica chimica acta》2011,377(1):34-41
Metal complexes have emerged as promising and novel scaffolds for the design of enzyme inhibitors. Reported herein are the design, synthesis, and evaluation of protein kinase inhibition properties of pyridocarbazole half-sandwich complexes containing P-donor ligands. The nature of the monodentate P-donor ligand has a strong effect on protein kinase binding properties, most likely due to a direct interaction with the glycine-rich loop in the ATP-binding site. We furthermore discovered that PMe3 pyridocarbazole complexes are interesting lead structures for the design of potent inhibitors for the protein kinase TrkA for which we obtained a nanomolar organometallic inhibitor. 相似文献
11.
Peter R. Craig Kevin R. Flower Warren R. Roper L. James Wright 《Inorganica chimica acta》1995,240(1-2):385-391
Treatment of MHCl(CO)(PPh3)3 (M=Ru, Os) with (CH2=CH)SnR3 is a good general route to the coordinatively unsaturated osmium and ruthenium stannyl complexes M(SnR3)Cl(CO)(PPh3)2 (1: M=Ru, R=Me; 2: M=Ru, R = n-butyl; 3: M=Ru, R = p-tolyl; 4: M=Os, R=Me). These coordinatively unsaturated complexes readily add CO and CN-p-tolyl to form the coordinatively saturated compounds M(SnR3)Cl(CO)L(PPh3)2 (5: M=Ru, R=Me, L=CO; 6: M=;Ru, R = n-butyl, L=CO; 7: M=Ru, R = p-tolyl, L=CO; 8: M=Os, R=Me, L=CO; 9: M=Ru, R=Me, L=CN-p-tolyl; 10: M=Ru, R = n-butyl, L=CN-p-tolyl; 11: M=Os, R=Me, L=CN-p-tolyl). In addition, the chloride ligand in Ru(SnR3)Cl(CO)(PPh3)2 proves to be labile and treatment with the potentially bidentate anionic ligands, dimethyldithiocarbamate or diethyldithiocarbamate, affords the coordinatively saturated compounds Ru(SnR3)(η2-S2CNR′2)(CO)(PPh3)2 (12: R=Me, R′ = Me; 13: R=Me, R′ = Et; 14: R = n-butyl, R′ = Me; 15: R = p-tolyl, R′ = Me; 16: R = p-tolyl, R′ = Et). Chloride is also displaced by carboxylates forming the six-coordinate compounds Ru(SnR3)(η2-O2CR′)(CO)(PPh3)2 (17: R=Me, R′ = H; 18: R=Me, R′ = Me; 19: R=Me, R′ = Ph; 20: R = n-butyl, R′ = Me; 21: R = p-tolyl, R′ = Me). IR and 1H NMR spectral data for all the new compounds and 31P and 119Sn NMR spectral data for selected compounds are reported. 相似文献
12.
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-H?Cl interactions in the solid state. 相似文献
13.
M. Helena Garcia Tânia S. Morais M. Fátima M. Piedade Virtudes Moreno Veronica Noe 《Journal of inorganic biochemistry》2009,103(3):354-361
Inhibition of the growth of LoVo human colon adenocarcinoma and MiaPaCa pancreatic cancer cell lines by two new organometallic ruthenium(II) complexes of general formula [Ru(η5-C5H5)(PP) L][CF3SO3], where PP is 1,2-bis(diphenylphosphino)ethane and L is 1,3,5-triazine (Tzn) 1 or PP is 2x triphenylphosphine and L is pyridazine (Pyd) 2 has been investigated. Crystal structures of compounds 1 and 2 were determined by X-ray diffraction studies. Atomic force microscopy (AFM) images suggest different mechanisms of interaction with the plasmid pBR322 DNA; while the mode of binding of compound 1 could be intercalation between base pairs of DNA, compound 2 might be involved in a covalent bond formation with N from the purine base. 相似文献
14.
Catalytic activity of dihydride ruthenium complexes in the hydrogenation of nitrogen containing heterocycles 总被引:1,自引:0,他引:1
Piero Frediani Valentina Pistolesi Marco Frediani Luca Rosi 《Inorganica chimica acta》2006,359(3):917-925
The catalytic activity of the dihydride ruthenium complexes, RuH2(CO)2(PnBu3)2, RuH2(CO)2(PPh3)2 and RuH2(PPh3)4, in the hydrogenation of nitrogen containing heterocycles has been tested by analyzing the influence of reaction parameters such as temperature, hydrogen pressure, catalyst concentration, on the rate and regioselectivity of the reaction.RuH2(PPh3)4 shows a better catalytic activity with an 86.7% conversion of quinoline after 24 h at 100 °C under a hydrogen pressure of 25 bar, while RuH2(CO)2(PPh3)2 and RuH2(CO)2(PnBu3)2 in the same conditions give a conversion of 37.1% and 35.6%, respectively. These results are confirmed by the reaction rate of the hydrogenation of quinoline, since the Kc in the presence of RuH2(PPh3)4 (1.46 × 10−5 s−1) is higher than others (6.37 × 10−6 s−1 for RuH2(CO)2(PPh3)2 and 6.36 × 10−6 s−1 for RuH2(CO)2(PnBu3)2).Noteworthy is the selectivity of these catalytic systems in the hydrogenation of quinoline: in all tests the three catalysts lead to 1,2,3,4-tetrahydroquinoline as the major product, furthermore this compound is the only formed in the presence of RuH2(CO)2(PPh3)2. The selectivity is affected by the presence of an acid (CH3COOH) or a base (NnBu3) in the reaction media.The complex RuH2(PPh3)4 is catalytically active, even if in a minor extent, in the hydrogenation of isoquinoline, pyridine and 2-methylpyridine.The basicity of the substrate and steric hindrance around the nitrogen atom show a great influence on the conversion.The results obtained suggest that the catalytic system activates a heterocyclic ring through the coordination of the heteroatom to the metal centre of the complexes. 相似文献
15.
The dinuclear complex [(η6-C6H6)Ru(μ-N3)Cl]2 (1) is obtained by the reaction of [(η6-C6H6)RuCl2]2 with sodium azide in ethanol. The benzene ruthenium β-diketonato complexes of the general formula [(η6-C6H6)Ru(L∩L)Cl] {L∩L = O,O′-acac (2); O,O′-bzac (3); O,O′-dbzm (4)} are obtained in methanol by the reaction of [(η6-C6H6)RuCl2]2 with the corresponding β-diketonates. These complexes further react with sodium azide in ethanol to yield complexes of the type [(η6-C6H6)Ru(L∩L)N3] [L∩L = O,O′-acac (5); L∩L = O,O′-bzac (6); L∩L = O,O′-dbzm (7)]. The complexes 5-7 are obtained as well by treating 1 with sodium salts of β-diketonates. These neutral benzene ruthenium azido complexes undergo [3+2] dipolar cycloaddition reaction with activated alkynes (MeO2CCCCO2Me, EtO2CCCCO2Et) or fumaronitrile (NCHCCHCN) to yield the corresponding benzene ruthenium triazolato complexes; [(η6-C6H6)Ru(O,O′-acac){N3C2(CO2Me)2}] (8), [(η6-C6H6)Ru(O,O′-acac){N3C2(CO2Et)2}] (9), [(η6-C6H6)Ru(O,O′-acac){N3C2HCN}] (10), [(η6-C6H6)Ru(O,O′-bzac){N3C2HCN}] (11) and [(η6-C6H6)Ru(O,O′-dbzm){N3C2HCN}] (12). These complexes are fully characterized on the basis of microanalyses, FT-IR and FT-NMR spectroscopy. The molecular structure of [(η6-C6H6)Ru(O,O′- acac){N3C2(CO2C2H5)2}] (9) is confirmed by single crystal X-ray diffraction study. 相似文献
16.
Cyclopentadienyltricarbonyl tungsten selenocarboxylate complexes CpW(CO)3SeCOR (1) (R = C6H5 (a), 3,5-C6H3(NO2)2 (b), 3-C6H4NO2 (c), 4-C6H4NO2 (d), CH3 (e)) and cyclopentadienyltricarbonyl tungsten selenosulfonate complexes CpW(CO)3SeSO2R (2) (R = C6H5 (a), 4-C6H4CH3 (b), 4-C6H4OCH3 (c), 4-C6H4Cl (d), CH3 (e)) have been prepared from the tungsten anion [CpW(CO)3Se]− and acid- or sulfonyl chlorides respectively. The new complexes (1 and 2) have been characterized by IR, 1H NMR spectroscopies as well as elemental analysis. The crystal structure of CpW(CO)3SeCO-3-C6H4NO2 (1c) was determined. 相似文献
17.
We report here the synthesis, characterization and in vitro antiamoebic activity of 5-nitrothiophene-2-carboxaldehyde thiosemicarbazones (TSC), 1–5, and their bidentate complexes [Ru(η4-C8H12)(TSC)Cl2] 1a–5a. The biological studies of these compounds were investigated against HK-9 strain of Entamoeba histolytica and the concentration causing 50% cell growth inhibition (IC50) was calculated in the micromolar range. The ligands exhibited antiamoebic activity in the range (2.05–5.29 μM). Screening results indicated that the potencies of the compounds increased by the incorporation of ruthenium(II) in the thiosemicarbazones. The complexes 1a–5a showed antiamoebic activity with an IC50 of 0.61–1.43 μM and were better inhibitors of growth of E. histolytica, based on IC50 values. The most promising among them is Ru(II) complex 2a having 1,2,3,4-tetrahydroquinoline as N4 substitution. 相似文献
18.
The synthesis of four ruthenium phosphonium alkylidene complexes [(H2IMes)Cl2RuCH(PCy3)]+[A]− (1, A = B(C6F5)4; 2, A = BF4; 3, A = OTf; 4, A = BPh4), differing only in the anion is described. The X-ray structures of 1, 3 and 4 show them to be isostructural in the cation, with no interaction between the Ru centers and the anion. Ring closing metathesis of a substrate to a six-membered methylcyclohexene at 0 °C in CD2Cl2 using 1 mol% catalyst, shows that catalysts 1-4 behave very similarly, and exhibit superior activity in comparison to Grubbs second generation and fast-initiating catalysts. 相似文献
19.
A series of new ruthenium(II) carbonyl chloride complexes with pyridine-functionalised N-heterocyclic carbenes [Ru(Py-NHC)(CO)2Cl2], [Py-NHC = 3-methyl-1-(2-pyridyl)imidazol-2-ylidene, 1 (1a and 1b); 3-methyl-1-(2-picoyl)imidazol-2-ylidene, 2 (2a and 2b); 3-methyl-1-(2-pyridyl)benzimidazolin-2-ylidene, 3 (3b); 3-methyl-1-(2-picoyl)benzimidazolin-2-ylidene, 4 (4a and 4b); 1-methyl-4-(2-pyridyl)-1,2,4-triazoline-5-ylidene, 5 (5a and 5b)] have been prepared by transmetallation from the corresponding silver carbene complexes and characterized by NMR, IR spectroscopy and elemental analysis. In these complexes with bidentate Py-NHC ligands, one CO ligand is trans to the Py ligand. In 1a, 2a, 4a, and 5a, the NHC ligand is trans to the other CO ligand, thus leaving the two Cl− ligands trans to each other. In 1b, 2b, 3b, 4b, and 5b, the NHC ligands are trans to one Cl− ligand, and the two Cl− ligands are cis to each other. The structures for 1b, 2b, 3b and 4b have been determined by single-crystal X-ray diffraction. These complexes are efficient catalysts in the transfer hydrogenation of acetophenone and their catalytic activities are found to be influenced by electronic effect of the N-heterocyclic carbene ligands. 相似文献
20.
Nitric oxide plays an important role in various biological processes, such as neurotransmission, blood pressure control, immunological responses, and antioxidant action. The control of its local concentration, which is crucial for obtaining the desired effect, can be achieved with exogenous NO-carriers. Coordination compounds, in particular ruthenium(III) and (II) amines, are good NO-captors and -deliverers. The chemical and photochemical properties of several ruthenium amine complexes as NO-carriers in vitro and in vivo have been reviewed. These nitrosyl complexes can stimulate mice hippocampus slices, promote the lowering of blood pressure in several in vitro and in vivo models, and control Trypanosoma cruzi and Leishmania major infections, and they are also effective against tumor cells in different models of cancer. These complexes can be activated chemically or photochemically, and the observed biological effects can be attributed to the presence of NO in the compound. Their efficiencies are explained on the basis of the [RuIINO+]3+/[RuIINO0]2+ reduction potential, the specific rate constant for NO liberation from the [RuNO]2+ moiety, and the quantum yield of NO release. 相似文献