cas 52462-29-0, Dichloro(p-cymene)ruthenium(II) dimer

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A new photoactivatable ruthenium(II) complex with an asymmetric bis-thiocarbohydrazone: Chemical and biological investigations
The synthesis, photoactivation and biological activity of a new piano-stool Ru(II) complex is herein reported. The peculiarity of this complex is that its monodentate ligand which undergoes the photodissociation is an asymmetric bis-thiocarbohydrazone ligand that possesses a pyridine moiety binding to Ru(II) and the other moiety contains a quinoline that endows the ligand with the capacity of chelating other metal ions. In this way, upon dissociation, the ligand can be released in the form of a metal complex. In this article, the double ability of this new Ru(II) complex to photorelease the ligand and to chelate copper and nickel is explored and confirmed. The biological activity of this compound is studied in cell line A549 revealing that, after irradiation, proliferation inhibition is reached at very low half maximal inhibitory concentration (IC50) values. Further, biological assays reveal that the dinuclear complex containing Ni is internalized in cells.
Alinovi, Rossella,Bisceglie, Franco,Orsoni, Nicolò,Pelosi, Giorgio,Pinelli, Silvana,Pioli, Marianna,Scaccaglia, Mirco
(2021)
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Synthesis of Ruthenium Tris-Diimine Photosensitizers Substituted by Four Methylphosphonate Anchoring Groups for Dye-Sensitized Photoelectrochemical Cell Applications
The design and synthesis of ruthenium tris-diimine photosensitizers appropriately functionalized to be (i) anchored onto transparent conductive oxides (TCO) and (ii) covalently coupled with a water-splitting catalyst represents an important target for solar fuel production in dye-sensitized photoelectrochemical cells (DS-PECs). In this study, two different synthetic routes to prepare heteroleptic [Ru(4,4′-(CH2PO3Et2)2-bpy)2(N^N)](PF6)2 complexes are evaluated, the scope and limitations of the organometallic pathway involving half-sandwich η6-arene ruthenium complexes as synthetic intermediates being especially studied. The spectroscopic and electrochemical characterization of a series of novel structures varying by the nature of the third diimine N^N ligand is reported.
Queyriaux, Nicolas,Giannoudis, Emmanouil,Lefebvre, Jean-Fran?ois,Artero, Vincent,Chavarot-Kerlidou, Murielle
p. 2154 - 2161
(2019)
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Design, synthesis and in vitro bioactivity of mixed ligand Ru(II) complexes bearing the fluoroquinolone antibacterial agents
Mixed ligand Ru(II) phenanthroline complexes of the type [Ru(1,10-phen)2Flq]ClO4 (RPFlq-1-3) and “piano-stool”-type Ru(II) arene complexes [Ru(η6-p-cymene)Cl(Flq)] (RAFlq-1-3), where Flq = fluoroquinolone, have been synthesized, characterized and studied for their anticancer potential. DFT calculations were in line with the proposed structures, wherein the fluoroquinolones are coordinated to the metal through the ring carbonyl and one of the carboxylic oxygen?atoms in a bidentate fashion. Binding efficacies of the synthesized complexes with bovine serum albumin (BSA) and CT-DNA were studied spectroscopically, and it has been established that the arene complexes, though have moderate binding propensities to CT-DNA (Kb = 0.8–1.7 × 103?M?1), have 102–103-fold better binding efficacies toward BSA (Ka = 3.2 × 105–2.1 × 106?M?1) due to the presence of the hydrophobic arene moiety. These results further prompted a study in their in vitro cytotoxicity assay on A-549 non-small cell lung cancer and MCF7 breast cancer cell lines. Furthermore, gene expression studies on BAX and BCL-2 genes and FACS analysis confirmed apoptosis as the mode of cell death.
Pulipaka, Ramadevi,Dash, Soumya R.,Khanvilkar, Priyanka,Jana, Sarmita S.,Devkar, Ranjitsinh V.,Chakraborty, Debjani
p. 721 - 735
(2019)
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Microwave-assisted synthesis and DNA-binding studies of half-sandwich ruthenium(II) arene complexes containing phenanthroimidazole-triarylamine hybrids
A new series of half-sandwich Ru(II)-arene complexes with phenanthroimidazole-triarylamine hybrid ligands were synthesized and scrutinized for DNA binding studies. The metal complexes were prepared via microwave-assisted synthesis with high yield and purity. The interaction of Ru(II)-arene complex with calf thymus DNA was studied by spectrophotometric methods. All six complexes exhibited significant interaction with CT-DNA. Methoxyphenyl-substituted metal complex showed the highest binding efficiency with a binding constant (Kb) of 5.053 × 104 M?1 due to its electron-rich nature. The methoxyphenyl group remarkably enhanced the interaction through stabilization of π-orbital of the metal complex which resulted in the efficient coupling. Phenyl- and thiophene-substituted ligands also showed good binding constants of 4.908 × 104 M?1 and 4.509 × 104 M?1, respectively. The absorption and ethidium bromide displacement studies declare that both the intercalation and groove binding is anticipated by these complexes. These Ru(II) complexes with phenanthroimidazole-triarylamine hybrid ligands can be realized as efficient DNA binding agents.
Abhijna Krishna, Ramakrishnan,Dheepika, Ramachandran,Muralisankar, Mathiyan,Nagarajan, Samuthira
p. 838 - 849
(2021)
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Evaluation of biomolecular interactions and cytotoxic activity of organometallic binuclear Ru(II) complexes of ferrocenyl thiosemicarbazones
Four new ferrocenyl substituted thiosemicarbazone ligands (L1–L4) and their corresponding binuclear ruthenium(II) arene complexes of the general type [(η6-p cym)(L)Ru(μ-im)Ru(L)(η6-p-cym)]Cl (C1–C4) and [(η6-p cym)(L)Ru(μ-azpy)Ru(L)(η6-p-cym)]Cl2 (C5–C8) (cym = cymene, im = imidazole, azpy = 4,4′-azopyridine) have been synthesized and characterized. The structures of the complexes were established through DFT calculations and geometry optimization. The interactions of the binuclear complexes with DNA were investigated by absorption, emission and viscosity studies which indicated that the complexes bind to DNA via intercalation. Meanwhile, the interaction of complexes with the protein, bovine serum albumin (BSA), has also been studied using fluorescence emission spectroscopy. The experimental results show that the binuclear complexes exhibit good binding propensities to BSA. The complexes can quench the intrinsic fluorescence of BSA remarkably through a static or dynamic quenching process. In addition, the in?vitro cytotoxicity of complexes C1–C8 against HeLa cell line was assayed which showed lower IC50 values indicating their higher cytotoxicity and potency in killing the cancer cells at low concentrations. Communicated by Ramaswamy H. Sarma.
Khanvilkar, Priyanka,Dash, Soumya R.,Vohra, Alisagar,Devkar, Ranjitsinh,Chakraborty, Debjani
p. 6044 - 6055
(2021)
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Imidazole/4,4′-azopyridine bridging binuclear Ru(II) complexes: design, synthesis, bimolecular interactions and cytotoxicity against HeLa cell line
Binuclear Ru(II)-arene complexes [(η6-pcym)(Flq)Ru(μ-im/μ-azpy)Ru(Flq)(η6-p-cym)]Cl (C1–C8) (cym = cymene; Flq = fluoroquinolones; im = imidazole; azpy = 4,4′azo pyridine) have been synthesized and characterized by elemental analysis, molar conductivity and various spectral techniques (ESI-MS, IR, UV-Vis and 1H-NMR). The geometry of the complexes was optimized by DFT calculations, which revealed a pseudo-octahedral coordination around each metal centre. Binding of the synthesized complexes with CT-DNA and BSA was studied spectroscopically, and it has been established that the presence of two hydrophobic planar arene moieties enhances the binding efficacies of the binuclear complexes to the macromolecules, compared to their mononuclear analogues. The results of competitive binding between C1–C8 and ethidium bromide (EB) towards DNA have shown that the complexes are able to displace EB from DNA-EB adduct and interact with DNA via intercalation. The complexes display cytotoxicity against the HeLa human cervical cancer cell lines with IC50 values in the range of 30.1–120.9 μM.
Chakraborty, Debjani,Dash, Soumya R.,Devkar, Ranjitsinh,Khanvilkar, Priyanka,Pulipaka, Ramadevi,Shirsath, Kavita
p. 3313 - 3326
(2021)
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Mixed ligand ruthenium arene complexes containing N-ferrocenyl amino acids: Biomolecular interactions and cytotoxicity against MCF7 cell line
Synthesis, characterization, DNA and protein binding as well as anticancer activity of the organometallic complexes [Ru(η6-p-cym)(L)Cl] (where, p-cym?=?p-cymene MeC6H4Pri, L?=?N-ferrocenyl amino acid conjugates) RAFcA 1–4 have been described. The complexes 1–4 exhibited strong DNA/BSA binding and anticancer activity against breast cancer MCF7 cell line. Their binding with calf thymus DNA (CT DNA) and bovine serum albumin (BSA) have been examined by absorption and emission spectral studies. Strong interactions between complexes and CT-DNA have been affirmed by absorption spectral and EB displacement studies, while interaction with BSA via static quenching was explored by fluorescence titration. Cytotoxicity, apoptosis and in?vitro anticancer activity of 1–4 toward MCF7 cell line have been investigated by MTT assay. The IC50values (37.1?μM - 86.6?μM) were found to be distinctly lower than those of NAMI-A and RAPTA complexes for MCF7 cell line which was followed by gene expression studies to confirm apoptosis as the mode of cell death.
Ramadevi, Pulipaka,Singh, Rinky,Jana, Sarmita S.,Devkar, Ranjitsinh,Chakraborty, Debjani
p. 80 - 87
(2017)
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Coordination chemistry of the [Pt2(μ-S)2 (PPh3)4] metalloligand with π-hydrocarbon derivatives of d6 ruthenium(II), osmium(II), rhodium(III) and iridium(III)
The reactivity of [Pt2(μ-S)2 (PPh3)4] towards [RuCl2 (η6-arene)]2 (arene=C6 H6, C6Me6, p -MeC6 H4Pri = p-cymene), [OsCl2 (η6- p -cymene)]2 and [MCl2 (η5-C5Me5)]2 (M=Rh, Ir) have been probed using electrospray ionisation mass spectrometry. In all cases, dicationic products of the type [Pt2(μ-S)2(PPh3)4 ML]2+ (L=π-hydrocarbon ligand) are observed, and a number of complexes have been prepared on the synthetic scale, isolated as their BPh4- or PF6- salts, and fully characterised. A single-crystal X-ray structure determination on the Ru p-cymene derivative confirms the presence of a pseudo-five-coordinate Ru centre. This resists addition of small donor ligands such as CO and pyridine. The reaction of [Pt2(μ-S)2 (PPh3)4] with RuClCp(PPh3) 2 (Cp=η5-C5H5) gives [Pt2(μ-S)2(PPh3) 4RuCp]+. In addition, the reaction of [Pt2(μ-S)2(PPh3)4] with the related carbonyl complex [RuCl2(CO)3] 2, monitored by electrospray mass spectrometry, gives [Pt2(μ-S)2(PPh3)4 Ru(CO)3Cl]+.
Audi Fong,Andy Hor,Henderson, William,Nicholson, Brian K.,Gardyne, Stephen,Devoy, Sarah M.
p. 24 - 31
(2003)
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Anticancer activity of hydrogen-bond-stabilized half-sandwich Ru II complexes with heterocycles
Neutral half-sandwich organometallic ruthenium(II) complexes of the type [(n6-cymene)RuCl2(L)] (H1-H10), where L represents a heterocyclic ligand, have been synthesized and characterized spectroscopically. The structures of five complexes were also established by single-crystal X-ray diffraction confirming a piano-stool geometry with n6 coordination of the arene ligand. Hydrogen bonding between the N-H group of the heterocycle and a chlorine atom attached to Ru stabilizes the metal-ligand interaction. Complexes coordinated to a mercaptobenzothiazole framework (H1) or mercaptobenzoxazole (H6) showed high cytotoxicity against several cancer cells but not against normal cells. In vitro studies have shown that the inhibition of cancer cell growth involves primarily G1-phase arrest as well as the generation of reactive oxygen species (ROS). The complexes are found to bind DNA in a non-intercalative fashion and cause unwinding of plasmid DNA in a cell-free medium. Surprisingly, the cytotoxic complexes H1 and H6 differ in their interaction with DNA, as observed by biophysical studies, they either cause a biphasic melting of the DNA or the inhibition of topoisomerase-IIα activity, respectively. Substitution of the aromatic ring of the heterocycle or adding a second hydrogen-bond donor on the heterocycle reduces the cytotoxicity. Copyright
Mitra, Raja,Das, Sangeeta,Shinde, Sridevi V.,Sinha, Sarika,Somasundaram, Kumaravel,Samuelson, Ashoka G.
p. 12278 - 12291
(2012)
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Organometallic binuclear Ru(II) complexes: Design, synthesis, DNA/BSA binding interactions and in-vitro cytotoxicity against HeLa cell line
Synthesis, characterization, DNA/BSA binding and cytotoxicity of organometallic binuclear Ru (II) complexes [(p-cym)(Fc-AA)Ru(μ-Im)Ru(Fc-AA)(p-cym)]Cl (C1–C4; where: p-cym = p-cymene MeC6H4Pri, Fc-AA = N-ferrocenyl amino acid conjugates (Fc-tyr1, Fc-phe2, Fc-leu3, Fc-trp4) and Im = Imidazole) have been described. The complexes C1–C4 exhibited strong DNA/BSA binding affinity and cytotoxicity against human cervical cancer HeLa cell line. Their binding with calf thymus CT-DNA and bovine serum albumin BSA have been examined by absorption and emission spectral studies. Intercalative interactions between complexes and CT-DNA have been affirmed by EB displacement studies and DNA viscosity measurements, while interaction with BSA via static quenching was explored by fluorescence titration. The anti-cancer activity of C1–C4 was studied using MTT assay on HeLa cell line and the corresponding IC50 values were calculated. The IC50 value (30.0 μM–120.0 μM) obtained were further compared with the well-known ruthenium complex NAMI-A, currently under phase II clinical trials which has IC50 value 608.5 μM.
Khanvilkar, Priyanka,Pulipaka, Ramadevi,Shirsath, Kavita,Devkar, Ranjitsinh,Chakraborty, Debjani
p. 134 - 140
(2019)
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The synthesis, structural characterization, and in vitro anti-cancer activity of chloro(p-cymene) complexes of ruthenium(II) containing a disulfoxide ligand
Two diruthenium(II) complexes [RuCl2(p-cymene)]2(μ-BESE) (1), [RuCl2(p-cymene)]2(μ-BESP) (2), and the mononuclear salt [RuCl(p-cymene)(BESE)]PF6 (3), containing the disulfoxides BESE and BESP, were synthesized and characterized by elemental analysis, and NMR and IR spectroscopies, and were shown to contain S-bound sulfoxide groups; the disulfoxides are EtS(O)(CH2)nS(O)Et, where n=2 (BESE) or 3 (BESP). Complexes 1 and 3 were also characterized by X-ray crystallography. Preliminary in vitro tests of 1 and 3 were conducted using the MTT assay, which measures mitochondrial dehydrogenase activity as an indication of cell viability; these complexes showed in vitro anti-cancer activity against a human mammary cancer cell line (MDA-MB-435s) with IC50 values of 360 and 55 μM, respectively.
Huxham, Lynsey A.,Cheu, Elizabeth L.S.,Patrick, Brian O.,James, Brian R.
p. 238 - 246
(2003)
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New organometallic ruthenium(ii) complexes with purine analogs - a wide perspective on their biological application
Three half-sandwich organometallic ruthenium(ii) complexes containing purine analogs such as triazolopyrimidines of general formula [(η6-p-cym)Ru(L)Cl2], wherep-cym representsp-cymene and L is 5,6,7-trimethyl-1,2,4-triazolo[1,5-a]pyrimidine (tmtp for1), 5,7-diethyl-1,2,4-triazolo[1,5-a]pyrimidine (detp for2) and 5-methyl-1,2,4-triazolo[1,5-a]pyrimidin-7(4H)-one (HmtpO for3), have been synthesized and characterized by elemental analysis, infrared, multinuclear magnetic resonance spectroscopic techniques (1H,13C,15N), and single-crystal X-ray diffraction (for1and2). All these complexes have been thoroughly screened for theirin vitrocytotoxicity against MCF-7 and HeLa cell lines as well as L929 murine fibroblast cells, indicating [(η6-p-cym)Ru(HmtpO)Cl2] (3) as the most active representative against the HeLa cell line and simultaneously being 64-fold less toxic to normal L929 murine fibroblast cells than cisplatin. At the same time,3has shown antimetastatic activity comparable to NAMI-A against HeLa cells both after 24 and 48 h of treatment in a wound healing assay. In order to better understand the mechanism of anticancer action and differences in the cytotoxic activity of1-3, the studies were expanded to determining their lipophilicity, the kinetic stability at pH 6.5-8, the effect on reactive oxygen species (ROS) production in HeLa cells and interactions with significant biomolecules (DNA and albumin) by using molecular docking and circular dichroism (CD) experiments. Furthermore, antiparasitic studies againstL. braziliensis,L. infantumandT. cruzireveal that the newly synthesized complexes1-3are very promising candidates which can compete with commercial antiparasitic drugs. Complex3in particular, on top of exhibiting a high antiparasitic effect (IC50a selectivity index >1000.
Fandzloch, Marzena,J?drzejewski, Tomasz,Dobrzańska, Liliana,Esteban-Parra, Ginés M.,Wi?niewska, Joanna,Paneth, Agata,Paneth, Piotr,Sitkowski, Jerzy
p. 5557 - 5573
(2021)
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Selective Targeting of the Zinc Finger Domain of HIV Nucleocapsid Protein NCp7 with Ruthenium Complexes
Nucleocapsid protein 7 (NCp7) is an attractive target for anti-HIV drug development. Here we found that ruthenium complexes are reactive to NCp7 and various Ru-agents exhibit significantly different reactivity. Interestingly, the zinc-finger domains of NCp7 also demonstrate different affinity to Ru-complexes; the C-terminal domain is much more reactive than the N-terminal domain. Each zinc-finger domain of NCp7 binds up to three Ru-motifs, and the ruthenium binding causes zinc-ejection from NCp7 and disrupts the protein folding. Therefore, ruthenium complexes interfere with the DNA binding of NCp7 and interrupt the protein function. The different reactivity of Ru-agents suggests a feasible strategy for improving the targeting of NCp7 by ligand design. This work provides an insight into the mechanism of ruthenium complex with NCp7, and suggests more potential application of ruthenium drugs.
Sheng, Yaping,Cao, Kaiming,Li, Ji,Hou, Zhuanghao,Yuan, Siming,Huang, Guangming,Liu, Hongke,Liu, Yangzhong
p. 19146 - 19151
(2018)
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Bis(arene) complexes of RuII. Synthesis, crystal structure and electrochemical behavior of 6-p-isopropyltoluene)Ru>2
Cleavage of the chloro-bridged RuII dimer, 2 with AgBF4 in acetone and refluxing the product in trifluoroacetic acid with an excess of p-isopropyltoluene leads to the formation of the dicationic bis(arene) RuII complex, 2, in nearly quantitative yield.Strong upfield shifts are observed in the 13C NMR spectrum of the arene carbon atoms of p-isopropyltoluene following coordination and an investigation of the electrochemistry of this complex shows that it undergoes an irreversible reduction in nitromethane solvent at -0.78 V versus an Ag/AgCl reference electrode.An X-ray crystal structure determination of the complex shows that the complex consists of a RuII center located between two p-isopropyltoluene ligands that are coordinated in an η6 manner.The arene rings are separated by a distance of 3.450 Angstroem and are essentially coplanar with a dihedral angle of 178.4o.The crystals are monoclinic, space group P21/n wth lattice constants a=10.094(2) Angstroem, b=12.996(3) Angstroem, c=17.371(3) Angstroem, β=94.90(1)o and V=2270.4(8) Angstroem3.Convergence to conventional R values of R=0.0711 and Rw=0.0854 with a goodness-of-fit of 1.15 was obtained for 280 variable parameters and 2976 reflections with I > 0?(I).
Suravajjala, Sandhya,Polam, Jayapal Reddy,Porter, Leigh Christopher
p. 201 - 206
(1993)
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Antiparasitic activity and ultrastructural alterations provoked by organoruthenium complexes against: Leishmania amazonensis
Four new organoruthenium complexes with formula [RuCl(η6-p-cymene)(μ-FCZ)]2[Cl]2 (1), [RuCl(FCZ)(η6-p-cymene)(PPh3)]PF6 (2), [RuCl(CTZ)(η6-p-cymene)(PPh3)]PF6 (3) and [RuCl(KTZ)(η6-p-cymene)(PPh3)]PF6 (4) (where FCZ: 2-(2,4-difluorophenyl)-1,3-di(1H-1,2,4-triazol-1-yl)-2-propanol, CTZ: 1-[(2-chlorophenyl)-diphenylmethyl-1H-imidazole] and KTZ: cis-1-acetyl-4-[4-[[2-(2,4-dichlorophenyl)-2-(1H-imidazol-1-ylmethyl)-1,3-dioxolan-4-yl]methoxy]phenyl]piperazine) were synthesized, characterized and evaluated as potential inhibitors for Leishmania amazonensis growth by widely reported methods. Complexes 3 and 4 displayed effective IC50 activities against Leishmania amazonensis promastigotes and intracellular amastigotes in the range of nanomolar concentration. Scanning and transmission electron microscopy analysis of Leishmania amazonensis promastigotes after treatment with 300 or 500 nM of complexes 3 and 4 for 48 h showed morphological alterations in the cell surface, a shortening of the flagellum, loss of mitochondrial matrix, disorganization of the kDNA and abnormal chromatin condensation. Thus, our strategy of incorporating a ruthenium atom into the structure of clinical drugs to improve their efficacy continues to demonstrate suitability for metallodrug discovery purposes.
Colina-Vegas, Legna,Lima Prado Godinho, Joseane,Coutinho, Thallita,Correa, Rodrigo S.,De Souza, Wanderley,Cola Fernandes Rodrigues, Juliany,Batista, Alzir Azevedo,Navarro, Maribel
p. 1431 - 1439
(2019)
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Synthesis, Structure and Cytotoxicity of N,N and N,O-Coordinated RuII Complexes of 3-Aminobenzoate Schiff Bases against Triple-negative Breast Cancer
Half-sandwich RuII complexes, [(YZ)RuII(η6-arene)(X)]+, (YZ=chelating bidentate ligand, X=halide), with N,N and N,O coordination (1–9) show significant antiproliferative activity against the metastatic triple-negative breast carcinoma (MDA-MB-231). 3-aminobenzoic acid or its methyl ester is used in all the ligands while varying the aldehyde for N,N and N,O coordination. In the N,N coordinated complex the coordinated halide(X) is varied for enhancing stability in solution (X=Cl, I). Rapid aquation and halide exchange of the pyridine analogues, 2 and 3, in solution are a major bane towards their antiproliferative activity. Presence of free ?COOH group (1 and 4) make complexes hydrophilic and reduces toxicity. The imidazolyl 3-aminobenzoate based N,N coordinated 5 and 6 display better solution stability and efficient antiproliferative activity (IC50 ca. 2.3–2.5 μM) compared to the pyridine based 2 and 3 (IC50>100 μM) or the N,O coordinated complexes (7–9) (IC50 ca. 7–10 μM). The iodido coordinated, 6, is resistant towards aquation and halide exchange. The N,O coordinated 7–9 underwent instantaneous aquation at pH 7.4 generating monoaquated complexes stable for at least 6 h. Complexes 5 and 6, bind to 9-ethylguanine (9-EtG) showing propensity to interact with DNA bases. The complexes may kill via apoptosis as displayed from the study of 8. The change in coordination mode and the aldehyde affected the solution stability, antiproliferative activity and mechanistic pathways. The N,N coordinated (5 and 6) exhibit arrest in the G2/M phase while the N,O coordinated 8 showed arrest in the G0/G1 phase.
Mukherjee, Arpan,Koley, Tuhin Subhra,Chakraborty, Ayan,Purkait, Kallol,Mukherjee, Arindam
supporting information
p. 3729 - 3742
(2021/10/14)

Phosphine ligands in the ruthenium-catalyzed reductive amination without an external hydrogen source
A systematic study of the phosphine additives influence on the activity of a ruthenium catalyst in reductive amination without an external hydrogen source was carried out. [CymeneRuCl2]2 was used as a reference catalyst, and a broad set of phosphines including Alk3P, Alk2ArP, Ar3P and X3P was screened. Three complexes of general formula (Cymene)RuCl2PR3 were isolated in a pure form, and their catalytic activity was compared with the in situ generated complexes. Nonhindered triarylphosphines with electron acceptor groups were found to be the most perspective activating agents, increasing the activity of the catalyst approx. six times, Alk2ArP ligands have less noticeable influence, while trialkylphosphines strongly deactivate the ruthenium catalyst.
Makarova, Maria,Afanasyev, Oleg I.,Kliuev, Fedor,Nelyubina, Yulia V.,Godovikova, Maria,Chusov, Denis
(2021/04/15)

Synthesis, structure, spectral, redox properties and anti-cancer activity of Ruthenium(II) Arene complexes with substituted Triazole Ligands
Three versatile half-sandwich ruthenium(II) p-cymene complexes bearing substituted triazole ligands exhibit promising cancer cell growth inhibition activity towards A549 lung adenocarcinoma and MDA-MB-231 breast adenocarcinoma cells. In this context, the triazole based phthalimide protected new ligand (2-(3, 5-di(pyridin-2-yl)-4H-1,2,4-triazol-4-yl) isoindoline-1,3-dione) (L1) was prepared. Three ruthenium(II) p-cymene complexes [Ru(η6-p-cymene)(L1)Cl]Cl: [1]Cl, L1: (2-(3,5-di(pyridin-2-yl)-4H-1,2,4-triazol-4-yl)isoindoline-1,3-dione), [Ru(η6-p-cymene)(L2)Cl]Cl: [2]Cl and [Ru(η6-p-cymene)(L2)Cl](PF6): [2](PF6), L2 (2,2′-(4-(1H-pyrrol-1-yl)-4H-1,2,4-triazole-3,5-diyl) dipyridine) have been successfully synthesized and characterized by different spectral and analytical tools. Pyrrole protected substituted ruthenium complexes [2]Cl and [2](PF6) have been successfully identified structurally by single-crystal X-ray diffraction studies and confirmed the successful anion exchange. The redox properties of the ligands and the targeted metal complexes have been carefully examined. Cellular staining, live-cell imaging and MTT assay have been performed for all the complexes. We have demonstrated that our synthesized ruthenium(II) p-cymene complexes are capable of inducing significant cytotoxicity in A549 lung cancer cell lines, with an IC50 values of 6.56 ± 0.31 μM, 4.74 ± 0.2 μM and 13.67 ± 0.64 μM and in MDA-MB-231 breast cancer cell lines with an IC50 values of 1.13 ± 0.046 μM, 0.36 ± 0.016 μM and 11.32 ± 0.49 μM for [1]Cl, [2]Cl and [2](PF6) respectively.
Giri, Bishnubasu,Gupta, Parth,Karumban, Kalai Selvan,Kumbhakar, Sadananda,Maji, Somnath,Misra, Ashish,Muley, Arabinda,Raut, Rajnikant
supporting information

(2021/09/20)

Para -Selective hydroxylation of alkyl aryl ethers
para-Selective hydroxylation of alkyl aryl ethers is established, which proceeds with a ruthenium(ii) catalyst, hypervalent iodine(iii) and trifluoroacetic anhydride via a radical mechanism. This protocol tolerates a wide scope of substrates and provides a facile and efficient method for preparing clinical drugs monobenzone and pramocaine on a gram scale.
Zhu, Runqing,Sun, Qianqian,Li, Jing,Li, Luohao,Gao, Qinghe,Wang, Yakun,Fang, Lizhen
supporting information
p. 13190 - 13193
(2021/12/16)

Cationic half-sandwich ruthenium (II) complexes ligated by pyridyl-triazole ligands: Transfer hydrogenation and mechanistic studies
A series of novel cationic ruthenium half-sandwich complexes, bearing 1-substituted-4-pyridyl-1H-1,2,3-triazole ligands, were synthesized and fully characterized by a range of analytical techniques. The complexes were found to be efficient catalyst precursors for transfer hydrogenation reactions using ketones as substrates. We demonstrated that the complexes could hydrogenate acetophenone in excellent conversions (～75 %) within 3 h, employing a low concentration of base of only 2 mol %. Extending the reaction time to 6 h gave near quantitative conversions for both catalysts employed. In addition to this, the transfer hydrogenation of acetophenone was also found to proceed even at low catalyst loadings (0.025–0.05 mol%) and low base concentrations (0.25–1.0 mol%). Under these conditions substrate conversion was moderate (22–60 %). The catalytic efficiency of the most effective catalyst was then evaluated in the transfer hydrogenation of a small library of aromatic and aliphatic ketones. It was shown that more challenging substrates such as benzophenone and 2-octanone could be hydrogenated to the corresponding secondary alcohols in conversions > 90 %. Finally, based on several experimental observations, a possible mechanism for the process is proposed.
Joseph, M. C.,Mapolie, S. F.,Swarts, A. J.
supporting information

(2021/11/30)

Enantioselective transfer hydrogenation of pro-chiral ketones catalyzed by novel ruthenium and iridium complexes of well-designed phosphinite ligand
The interaction of [Ru(η6-arene)(μ-Cl)Cl]2 and Ir(η5-C5Me5)(μ-Cl)Cl]2 with a new Ionic Liquid-based phosphinite ligand, [(Ph2PO)-C6H9N2Ph]Cl, (2) gave [Ru((Ph2PO)-C6H9N2Ph)(η6-p-cymene)Cl2]Cl (3), [Ru((Ph2PO)-C6H9N2Ph)(benzene)Cl2]Cl (4) and [Ir((Ph2PO)-C6H9N2Ph)(C5Me5)Cl2]Cl (5), complexes. All the compounds were characterized by a combination of multinuclear NMR and IR spectroscopy as well as elemental analysis. Furthermore, the Ru(II) and Ir(III) catalysts were applied to asymmetric transfer hydrogenation of acetophenone derivatives using 2-propanol as a hydrogen source. The results showed that the corresponding alcohols could be obtained with good activity (up to 55% ee and 99% conversion) under mild conditions. Notably, [Ir((Ph2PO)-C6H9N2Ph)(C5Me5)Cl2]Cl (5) is more active than the other analogous complexes in the transfer hydrogenation (up to 81% ee).
Arslan, Nevin
p. 628 - 637
(2020/01/02)

Triphenylamine/carbazole-modified ruthenium(ii) Schiff base compounds: Synthesis, biological activity and organelle targeting
Four triphenylamine/carbazole-modified half-sandwich ruthenium(ii) compounds [(η6-p-cymene)Ru(N/O^N)Cl]0/+ with Schiff base chelating ligands (N/O^N) are synthesized and characterized. The introduction of Schiff base units effectively increases the antitumor activity of these compounds (IC50: 1.70 ± 0.56-17.75 ± 3.10 μM), which, meanwhile, can inhibit the metastasis of tumor cells effectively. These compounds follow an energy-dependent cellular uptake mechanism, mainly accumulate in lysosomes to destroy their integrity, and then eventually promote apoptosis. In addition, these compounds can induce an increase of intracellular reactive oxygen species (ROS) levels and provide an antitumor mechanism of oxidation, which is confirmed by the decrease of mitochondrial membrane potential (MMP) and the catalytic oxidation of the coenzyme nicotinamide-adenine dinucleotide (NADH). All these indicate that these ruthenium(ii) compounds are expected to be dual-functional antitumor agents: anti-metastasis and lysosomal damage.
Chen, Shujiao,Ge, Xingxing,Huang, Jie,Liu, Tong,Liu, Xicheng,Liu, Zhe,Shao, Yue,Tian, Laijin,Wang, Qinghui,Yao, Meimei,Yuan, Xiang-Ai
supporting information
p. 8774 - 8784
(2020/07/10)

Coumarin ligand-containing semi-sandwich type metal complex and preparation method and application thereof
The invention discloses a coumarin ligand-containing semi-sandwich type metal complex. The structural formula of the coumarin ligand-containing semi-sandwich type metal complex is shown in the specification. The invention also discloses a preparation method and application of the coumarin ligand-containing semi-sandwich type metal complex. The complex has an anti-cancer effect, the drug effect ofthe complex is improved under illumination, and the complex is suitable for clinical treatment of breast cancer.
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Paragraph 0028; 0037-0038

(2020/09/16)

Potent half-sandwich Ru(Ⅱ) N^N (aryl-BIAN) complexes: Lysosome-mediated apoptosis, in vitro and in vivo anticancer activities
Herein a new series of organometallic half-sandwich Ru(Ⅱ) complexes bearing aryl-BIAN chelating ligands with various electron-withdrawing and electron-donating substituents have been developed as theranostic agents. All the complexes display much higher anti-proliferative potency than the clinical chemotherapeutic drug cisplatin towards seven cancer cell lines. The anti-proliferative efficacy of these complexes is correlated to their electron-withdrawing ability. Interestingly, complex Ru1 also potently suppresses cancer cell migration in vitro and effectively inhibit tumor growth in vivo in a CT26 colon cancer mouse xenograft model. Mechanisms of action studies display that Ru1 can favorably accumulate in lysosome and exerts anti-cancer potency by inducing a series of events related to lysosomal dysfunction in CT26 cells. Interestingly, inhibition of lysosomal enzymes leads to suppression of cytotoxicity and apoptosis induced by Ru1. Our results elucidate that complex Ru1 can elicit cytotoxicity through lysosome-mediated apoptosis in vitro and suppress tumor growth in vivo.
Xu, Zhishan,Huang, Jie,Kong, Deliang,Yang, Yuliang,Guo, Lihua,Jia, Xianglei,Zhong, Genshen,Liu, Zhe
supporting information

(2020/09/02)

Aldehydes as Alkylating Agents for Ketones
Common and non-toxic aldehydes are proposed as reagents for alkylation of ketones instead of carcinogenic alkyl halides. The developed reductive alkylation reaction proceeds in the presence of the commercially available ruthenium catalyst [(cymene)RuCl2]2 (as low as 250 ppm) and carbon monoxide as the reducing agent. The reaction works well for a broad substrate scope, including aromatic and aliphatic aldehydes and ketones. It can be carried out without a solvent and often gives nearly quantitative yields of the products. This straightforward and cost-effective method is promising not only for laboratory application but also for industry, which produces carbon monoxide as a large-scale waste product.
Runikhina, Sofiya A.,Afanasyev, Oleg I.,Biriukov, Klim,Perekalin, Dmitry S.,Klussmann, Martin,Chusov, Denis
supporting information
p. 16225 - 16229
(2019/11/22)

Preparation method of ocene ruthenium complex and anti-tumor application thereof
The invention belongs to the field of research and development of anti-tumor medicines, and discloses a preparation method of an ocene ruthenium complex and anti-tumor application thereof by combiningwith DNA (deoxyribonucleic acid). A structure of an anion part of the ocene ruthenium complex is shown in a formula I. The preparation method has the advantages that the preparation technology of theocene ruthenium complex is simplified, the costs of raw materials are low, and the reaction time is short. The prepared ocene ruthenium complex has the advantages that the purity is high, the yield rate is high, the water solubility is good, and the spectrum property is excellent; the bonding ability of coordination with DNA base is realized, the bonding ability of DNA inserting via planar ligandis realized, and the strong DNA bonding function is realized; the growth of three types of tumor cells, such as human breast cancer cells MCF-7, human prostatic cancer cells 22Rv1 and human lung cancer cells A549, can be obviously inhibited, and a potential antitumor medicine with application value is realized.
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Paragraph 0017; 0019

(2019/02/04)

A Ru(II)-p-cymene compound bearing naproxen-pyridineamide. Synthesis, spectroscopic studies, computational analysis and in vitro anticancer activity against lung cells compared to Ru(II)-p-cymene-naproxen and the corresponding drug ligands
The design of new Ru(II) organometallics is a subject of interest to the field of anticancer metallodrugs. This work reports the interaction of the Ru(II)-η6-p-cymene framework with naproxen-pyridineamide (Npxpya, L1), a structurally modified form of the naproxen (HNpx, HL2) drug, to give the new organometallic [Ru(η6-p-cymene)(L1)Cl2] (1) bearing the Npxpya ligand. The reported naproxenate-derived, [Ru(η6-p-cymene)(L2)Cl] (2), is re-prepared, also from the precursor [Ru(η6-p-cymene)Cl2]2 (3), and additional investigation is performed. The two Ru(II)-arenes and the L1 ligand are fully characterized by ESI-MS, NMR, ATR/FT-IR and UV/VIS, and their structures corroborated by DFT computational calculations. Time-dependent 1H MNR studies show that both Ru(II)-arenes, despite being stable in non-coordinating solvents, undergo distinct step dissociation in dimethylsulfoxide solvent to give the corresponding drug ligands and [Ru(η6-p-cymene)(dmso)Cl2] (4) species. Electronic absorption spectroscopy experimental data show good correlation with DFT calculations. Organometallics 1 and 2, as well as their corresponding parent drug ligands, exhibit luminescence properties mainly associated to the naproxen moiety. Screening in NCI-H460 and A549 lung cancer cells reveals lack of activity for 2 and L2, while the new organometallic 1 is found to inhibit cell proliferation of both types of cell lines in similar way to the L1 drug. The structural modification, by inserting the pyridineamide moiety into the original structure of naproxen to form the Npxpya conjugated drug, is shown to be crucial for the anticancer activity. Compound 1, despite having IC50 close to the IC50 of L1, does not show significant effect on the mitochondrial membrane potential (MMP), in contrast to the behavior of the free L1 parent drug which significantly decreases the MMP in NCI-H460 cells. Interestingly, since 1H MNR studies indicate that organometallic 1 is completely dissociated in dmso (the solvent used to prepare the drug solutions for cell treatment in the biological assays) to give the L1 free drug and species 4, it is plausible to infer that the presence of Npxpya-free Ru species, probably in the form of species 4, might play a role in inhibiting the mechanism related to the mitochondrial function when the cells are treated with 1, in comparison with the cell treatment with the L1 free drug.
Tabares, Julie Pauline Gaitan,Santos, Rodrigo Luis S.R.,Cassiano, Jefferson Luiz,Zaim, Marcio H.,Honorato, Jo?o,Batista, Alzir A.,Teixeira, Sarah F.,Ferreira, Adilson Kleber,Viana, Rommel B.,Martínez, Sandra Quispe,Stábile, Antonio Carlos,de Oliveira Silva, Denise
supporting information
p. 27 - 38
(2019/02/17)

Aryl ruthenium complex for treating liver cancer and preparation method and application thereof
The invention discloses an aryl ruthenium complex having the structure as shown in the formula (I), and further provides a preparation method and application of the aryl ruthenium complex. The aryl ruthenium complex has high antineoplastic activity and ACE-inhibiting activity; the preparation method thereof is simple and low in cost, with low loss of raw materials.
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Paragraph 0033-0035

(2019/01/23)

Aryl ruthenium complex for preparing medicine for treating liver cancer and preparation method and use thereof
The invention discloses an aryl ruthenium complex for preparing a medicine for treating liver cancer and a preparation method and use thereof, and the chemical name of the aryl ruthenium complex is: (2-(4-(N-(5-diethylene glycol bis(2-Propynyl)ether) indazolylpiperidinyl))benzimidazolyl)-methylisopropylbenzene ruthenium (II), the structural formula is as shown in the specification. The aryl ruthenium complex contains benzimidazole and indazole heterocycle, has good biological activity, and also contains a large conjugated system, and the molecule is more stable.
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Paragraph 0036; 0038; 0039; 0041; 0043; 0045

(2019/01/24)

Synthesis, characterization and behavior in water/DMSO solution of Ru(II) arene complexes with bioactive carboxylates
The reactions of [RuCl(μ-Cl)(η6-p-cymene)]2 with sodium carboxylates, in methanol or acetonitrile solution, afforded the complexes [RuCl(κ2O-RCO2)(η6-p-cymene)] (RCO2 = valproate, 1; aspirinate, 2; diclofenate, 3), in 79–96% yields. Analogously, [RuCl(κ2O-dfCO2)(η6-benzene)], 4, was obtained in admixture with minor by-products from [RuCl(μ-Cl)(η6-benzene)]2 and sodium/silver diclofenate. The sequential reaction of [RuCl(μ-Cl)(η6-p-cymene)]2 with sodium salicylate and PPh3 gave [Ru(κ2O,O′-salCO2)(PPh3)(η6-p-cymene)], 5, in 70% yield. The hydride complex [Ru2Cl2(μ-Cl)(μ-H)(η6-p-cymene)2], 6, was produced in 36% yield from [RuCl(μ-Cl)(η6-p-cymene)]2 and sodium formate. An optimization of the experimental work-up allowed to isolate [RuCl(μ-Cl)(η6-p-cymene)]2 with an improved yield respect to the literature (98% vs. 65%). The bidentate coordination mode of the carboxylato ligands in 1–5 was unambiguously ascertained by IR and NMR spectroscopy, moreover the solid state structure of 1 was elucidated by single crystal X-ray diffraction. Complexes 1–3 experience rapid and quantitative dissociation of the carboxylato anion in DMSO/water/NaCl mixtures, mainly converting into [RuCl2(DMSO)(η6-p-cymene)], 7.
Biancalana, Lorenzo,Pampaloni, Guido,Zacchini, Stefano,Marchetti, Fabio
p. 201 - 211
(2018/07/06)

Organic ruthenium complex, preparation method thereof, and application thereof in preparation of antitumor drugs
The invention discloses an organic ruthenium complex and a preparation method thereof. The preparation method comprises the following steps: taking ruthenium trichloride hydrate and gamma-terpinene, dissolving the ruthenium trichloride hydrate and gamma-terpinene in ethanol, performing refluxing and stirring to obtain a compound I, taking 2-mercaptobenzimidazole and 7-bromoindazole, adding the 2-mercaptobenzimidazole and 7-bromoindazole into carbon tetrachloride, performing heating, then adding azobisisobutyronitrile and N-bromosuccinimide, carrying out a heat-insulation reaction, removing thecarbon tetrachloride, adding the compound I and toluene, dropwise adding a mixed solution of ethylenediamine, cesium carbonate and triethylamine while stirring, introducing nitrogen to remove oxygen,adding diethylene glycol bis(2-propynyl)ether, tetrakis(triphenylphosphine)palladium and copper iodide, carrying out a reaction at 80 DEG C, and dropwise adding hydrochloric acid until the obtained solution is neutral in order to precipitate a reddish brown solid that is the organic ruthenium complex. The invention also discloses an application of the organic ruthenium complex in the preparationof gastric cancer treatment drugs, liver cancer treatment drugs and hypertension treatment drugs. Experimental data basis is provided for the research and preparation of new medicines.
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Paragraph 0019; 0020; 0021; 0023; 0024; 0025; 0027-0029

(2019/01/08)

Aromatic ruthenium complex and its preparation method and application
The invention discloses a novel aromatic ruthenium complex. R1R2R3PIP is used as a main ligand. The R1, R2, and R3 are independently selected from -H, -Cl, -F, -Br, -I, -CF3, -NO2, -OCH3, -OH, -COOH,-CH3, -N(CH3)2, -C2H2, -SO2CH3, an alkyl group having 1 to 6 carbon atoms or a substituted alkyl group having 1 to 6 carbon atoms, phenyl or substituted phenyl, pyridyl or substituted pyridyl, furyl or substituted furyl, pyrrolyl or substituted pyrrolyl, and thiazolyl or substituted thiazolyl, wherein the substituents of phenyl, pyridyl, furyl and thiazolyl are independently selected from hydroxyl, nitro groups, halogens, amino groups, carboxyl, cyano groups, decyl groups, cycloalkyl groups having 3 to 8 carbon atoms, SO3H, alkyl having 1 to 6 carbon atoms, alkenyl having 2 to 6 carbon atoms,chain alkynyl having 2 to 6 carbon atoms, hydroxy(C1-C6)alkyl, amino(C1-C6)alkyl, CO2R', CONR'R', COR', SO2R'R', (C1-C6)alkoxy, (C1-C6)alkylthio group, -N(double bond)NR', NR'R' and trifluoro(C1 C6)alkyl.
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Paragraph 0104; 0105; 0106

(2018/03/25)

Aryl ruthenium complex for treating hypertension as well as preparation method and application thereof
The invention discloses aryl ruthenium complex for treating hypertension as well as a preparation method and application thereof. The aryl ruthenium complex is of a structure shown in a formula (1). The aryl ruthenium complex has extremely strong antineoplastic activity and an angiotensin converting enzyme inhibition activity effect, namely has effects of treating hypertension, stomach cancer andliver cancer and is novel and effective medicine which has the advantages of simple preparation method and low cost.
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Paragraph 0030; 0031

(2018/11/22)

Anti-tumor compound with phototoxicity and preparation method and application thereof
The invention provides an anti-tumor compound with phototoxicity, the chemical structural formula of which is shown in the description. The invention further discloses a preparation method and application of the anti-tumor compound with phototoxicity. The compound disclosed by the invention contains benzimidazole and indazole heterocycles, so the obtained compound has good bioactivity; and with alarge conjugated system, the molecules are more stable. The preparation method disclosed by the invention is simple, and has the advantage of low cost, the reaction process does not require a separation and purification process, raw material loss is reduced, and the requirement of green chemistry is met.
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Paragraph 0033; 0035; 0036; 0045

(2018/11/22)

Aryl ruthenium complex for treating stomach cancer as well as preparation method and application thereof
The invention discloses aryl ruthenium complex for treating stomach cancer as well as a preparation method and application thereof. The aryl ruthenium complex is of a structure shown in a formula (1).The aryl ruthenium complex has extremely strong antineoplastic activity and angiotensin converting enzyme inhibition activity effect, namely has effects of treating hypertension, stomach cancer and liver cancer and is novel and effective medicine which has the advantages of simple preparation method and low cost.
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Paragraph 0031; 0032

(2018/11/22)

Ruthenium (II) complex for treating liver cancer and preparation method and application thereof
The invention discloses a ruthenium (II) complex, which is characterized in that the ruthenium (II) complex has a structure as shown in the formula (1) in the specification. The invention also provides a preparation method and application of the ruthenium (II) complex. The ruthenium (II) complex has strong anti-tumor and ACE inhibitory activity. In addition, the preparation method is simple; costis low; and loss of raw materials is low.
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Paragraph 0025; 0026; 0027

(2018/11/27)

Aryl ruthenium complex used for preparing anti-tumor medicine and preparation method and application thereof
The invention discloses an aryl ruthenium complex used for preparing an anti-tumor medicine. A chemical name of the aryl ruthenium complex is monochloride dichloromono(2-(3-hydroxypropyl))-5-diethylene glycol bis(2-propinyl)ether-1-indazolyl benzimidazolyl)monomethylisopropyl benzeneruthenium (II), and a structural formula is as shown in the description. The invention further discloses a preparation method and multiple application of the aryl ruthenium complex. The aryl ruthenium complex contains benzimidazole and an indazole heterocyclic ring, has good biological activity and further containsa large conjugated system, so that molecules are more stable.
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Paragraph 0038; 0041; 0045

(2018/12/14)

Aryl ruthenium (II) complex used for treating gastric cancer and preparation method and application thereof
The invention discloses an aryl ruthenium (II) complex. The aryl ruthenium (II) complex has a structure as shown in the formula (1) as shown in the description. The invention further provides a preparation method and application of the aryl ruthenium (II) complex. The prepared aryl ruthenium (II) complex has high anti-tumor and ACE inhibiting activity, and the preparation method is simple, low incost and little in raw material loss.
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Paragraph 0034; 0035

(2018/12/14)

Half-Sandwich Iridium(III) and Ruthenium(II) Complexes Containing P^P-Chelating Ligands: A New Class of Potent Anticancer Agents with Unusual Redox Features
A series of half-sandwich IrIII pentamethylcyclopentadienyl and RuII arene complexes containing P^P-chelating ligands of the type [(Cpx/arene)M(P^P)Cl]PF6, where M = Ir, Cpx is pentamethylcyclopentadienyl (Cp?), or 1-biphenyl-2,3,4,5-tetramethyl cyclopentadienyl (CpxbiPh); M = Ru, arene is 3-phenylpropan-1-ol (bz-PA), 4-phenylbutan-1-ol (bz-BA), or p-cymene (p-cym), and P^P is 2,20-bis(diphenylphosphino)-1,10-binaphthyl (BINAP), have been synthesized and fully characterized, three of them by X-ray crystallography, and their potential as anticancer agents explored. All five complexes showed potent anticancer activity toward HeLa and A549 cancer cells. The introduction of a biphenyl substituent on the Cp? ring for the iridium complexes has no effect on the antiproliferative potency. Ruthenium complex [(η6-p-cym)Ru(P^P)Cl]PF6 (5) displayed the highest potency, about 15 and 7.5 times more active than the clinically used cisplatin against A549 and HeLa cells, respectively. No binding to 9-MeA and 9-EtG nucleobases was observed. Although these types of complexes interact with ctDNA, DNA appears not to be the major target. Compared to iridium complex [(η5-Cp?)Ir(P^P)Cl]PF6 (1), ruthenium complex (5) showed stronger ability to interfere with coenzyme NAD+/NADH couple through transfer hydrogenation reactions and to induce ROS in cells, which is consistent with their anticancer activities. The redox properties of the complexes 1, 5, and ligand BINAP were evaluated by cyclic voltammetry. Complexes 1 and 5 arrest cell cycles at the S phase, Sub-G1 phase and G1 phase, respectively, and cause cell apoptosis toward A549 cells.
Li, Juanjuan,Tian, Meng,Tian, Zhenzhen,Zhang, Shumiao,Yan, Chao,Shao, Changfang,Liu, Zhe
p. 1705 - 1716
(2018/02/27)

Ruthenium compound, preparation method therefor, precursor composition for film deposition containing same, and method for depositing film by using same
The present disclosure relates to a novel ruthenium compound, a method for preparing the ruthenium compound, a precursor composition for depositing a ruthenium-containing film including the ruthenium compound, and a method for depositing a ruthenium-containing film by using the precursor composition.
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Page/Page column 12; 13

(2018/05/16)

Half-Sandwich Iridium and Ruthenium Complexes: Effective Tracking in Cells and Anticancer Studies
Half-sandwich metal-based anticancer complexes suffer from uncertain targets and mechanisms of action. Herein we report the observation of the images of half-sandwich iridium and ruthenium complexes in cells detected by confocal microscopy. The confocal microscopy images showed that the cyclopentadienyl iridium complex 1 mainly accumulated in nuclei in A549 lung cancer cells, whereas the arene ruthenium complex 3 is located in mitochondria and lysosomes, mostly in mitochondria, although both complexes entered A549 cells mainly through energy-dependent active transport. The nuclear morphological changes caused by Ir complex 1 were also detected by confocal microscopy. Ir complex 1 is more potent than cisplatin toward A549 and HeLa cells. DNA binding studies involved interaction with the nucleobases 9-ethylguanine, 9-methyladenine, ctDNA, and plasmid DNA. The determination of bovine serum albumin binding was also performed. Hydrolysis, stability, nucleobase binding, and catalytic NAD+/NADH hydride transfer tests for complexes 1 and 3 were also carried out. Both complexes activated depolarization of mitochondrial membrane potential and intracellular ROS overproduction and induced cell apoptosis. Complex 3 arrested the cell cycle at the G0/G1 phase by inactivation of CDK 4/cyclin D1. This work paves the way to track and monitor half-sandwich metal complexes in cells, shines a light on understanding their mechanism of action, and indicates their potential application as theranostic agents.
Li, Juanjuan,Guo, Lihua,Tian, Zhenzhen,Zhang, Shumiao,Xu, Zhishan,Han, Yali,Li, Ruixia,Li, Yan,Liu, Zhe
p. 13552 - 13563
(2018/10/20)

Ruthenium complex containing N-heterocycle as well as preparation method and application
The invention discloses a ruthenium complex containing N-heterocycle, the structural formula of the ruthenium complex containing N-heterocycle is shown as formula (I) in the following description. Theruthenium complex containing N-heterocycle has stronger anti-tumor activity, has a good prospect of application to the treatment of gastric cancer and liver cancer and the like.
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Paragraph 0032; 0033

(2018/12/14)

HETERODINUCLEAR PLATINUM-RUTHENIUM COMPLEXES, PREPARATION THEREOF AND THERAPEUTIC USE THEREOF
A novel class of heterodinuclear Pt—Ru complexes are provided, and the methods for preparing the complexes are described. The inhibitory activities of the heterodinuclear Pt—Ru complexes against cancer/tumor cell growth, including cancer/tumor cells having a resistance to cisplatin, are further demonstrated.
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Paragraph 0035

(2017/03/21)

New functional chiral P-based ligands and application in ruthenium-catalyzed enantioselective transfer hydrogenation of ketones
Metal-catalyzed asymmetric transfer hydrogenation is a powerful and practical method for the reduction of ketones to produce the corresponding secondary alcohols, which are valuable building blocks in the pharmaceutical, perfume, and agrochemical industries. Hence, a series of novel chiral β-amino alcohols were synthesized by chiral amines with regioselective ring opening of (S)-propylene oxide or reaction with (S)-(+)-2-hydroxypropyl p-toluenesulfonate by a straightforward method. The chiral ruthenium catalytic systems generated from [Ru(arene)(μ-Cl)Cl]2 complexes and chiral phosphinite ligands based on amino alcohol derivatives were employed in asymmetric transfer hydrogenation of ketones to give the corresponding optically active alcohols; (2S)-1-{[(2S)-2-[(diphenylphosphanyl)oxy]propyl][(1R)-1-phenylethyl]amino}propan-2-yldiphenylphosphinitobis[dichol-oro(η6-benzene)ruthenium(II)] acts an excellent catalyst in the reduction of α-naphthyl methyl ketone, giving the corresponding alcohol with up to 99% ee. The substituents on the backbone of the ligands were found to have a remarkable effect on both the conversion and enantioselectivity of the catalysts. Furthermore, this transfer hydrogenation is characterized by low reversibility under these conditions.
Meri?, Nermin,Kayan, Cezmi,Gürbüz, Nevin,Karakaplan, Mehmet,Binbay, Nil Ertekin,Aydemir, Murat
p. 1739 - 1749
(2017/10/26)

Synthesis of the [(η6-p-cymene)Ru(dppb)Cl]PF6 complex and catalytic activity in the transfer hydrogenation of ketones
Catalysis under mild conditions is of great importance to various chemistry areas, particularly for the development of novel active compounds and for natural products modifications, among others. In this study, the synthesis, characterization, and evaluation of the catalytic activity of a new ruthenium(II) compound, [(η6-p-cymene)Ru(dppb)Cl]PF6 (A) where dppb=1,4-bis(diphenylphosphine)butane, is presented. Catalytic activity of the new Ru(II) compound was tested on hydrogen transfer reaction in various substrates, acetophenone, benzophenone, cyclohexanone, and methyl-ethyl-ketone. Potassium hydroxide was used as base, whereas isopropanol served as both solvent and hydrogen source. Samples comprising substrate: base: catalyst at a 200 : 20 : 1 ratio were poured into 5?mm tubes and monitored in situ at 40, 50, and 60?°C in a 600?MHz NMR spectrometer. The complex was active in the transfer hydrogenation of ketones, achieving conversions superior to 90% within 4?h at 60?°C, which suggests under mild conditions. Therefore, in situ monitoring the reactions through 1H NMR was a valuable technique to establish the possible catalytic mechanism of Ru(II) precatalyst.
Higuera-Padilla, Angel Ruben,Batista, Alzir Azevedo,Colina-Vegas, Legna,Villarreal, Wilmer,Colnago, Luiz Alberto
p. 3541 - 3551
(2017/10/31)

Phthalocyanine-aryl ruthenium compound and preparation method and application thereof
The invention discloses phthalocyanine-aryl ruthenium compound, namely mono-Beta-mono-2-(2-diethylamine)ethoxy-phthalocyaninemonomethylcumeneruthenium monochloride (II). The invention also discloses a preparation method of the phthalocyanine-aryl ruthenium compound; the preparation method comprises: 1) dissolving RuCl3.xH2O and Gamma-terpinene in absolute ethyl alcohol, heating for refluxing and stirring, standing and separating out to obtain dichloro-di-methylcumeneruthenium dichloride (II); 2) dissolving Beta-mono-nitro-phthalocyanine and 2-(2-diethylamine)ethanol in DMF (dimethyl formamide) solution, reacting under nitrogen protection, and standing and separating out to obtain Beta-mono-2-(2-diethylamine)ethoxy-phthalocyanine; 3) dissolving the Beta-mono-2-(2-diethylamine)ethoxy-phthalocyanine and the dichloro-di-methylcumeneruthenium dichloride (II) in absolute ethyl alcohol, heating and stirring for refluxing, reacting, adding n-hexane, and separating out red crystal which is the product mono-Beta-mono-2-(2-diethylamine)ethoxy-phthalocyaninemonomethylcumeneruthenium monochloride (II). The invention also discloses application of the phthalocyanine-aryl ruthenium compound.
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Paragraph 0036; 0037; 0038; 0039

(2017/05/25)

Phthalocyanine-aryl ruthenium compound and preparation method and application thereof
The invention discloses a phthalocyanine-aryl ruthenium compound. The phthalocyanine-aryl ruthenium compound is 1-chlo-1-beta-phthalocyanine-5-phenanthroline ether-1-methylisopropyl benzene synthetic ruthenium (II). The invention further discloses a preparation method of the phthalocyanine-aryl ruthenium compound. The preparation method comprises the steps that 1, RuCl3.xH2O and gamma-terpinene are dissolved in absolute ethyl alcohol, heating reflux is carried out, still standing is carried out, and dichloride dichloro-2-methylisopropyl benzene synthetic ruthenium (II) is separated out; 2, beta-1-hydroxy-phthalocyanine, 5-bromine-1,10-orthophenanthrolene and cesium carbonate are taken to be dissolved in a DMF solution, reacting is carried out at the temperature of 80 DEG C under nitrogen shielding, still standing is carried out, and beta-phthalocyanine-5-orthophenanthrolene ether is separated out; 3, beta-phthalocyanine-5-orthophenanthrolene ether and dichloride dichloro-2-methylisopropyl benzene synthetic ruthenium (II) are dissolved in absolute ethyl alcohol, heating, stirring and reflux are carried out, the solution is evaporated till 2 ml of liquid is left after the reaction is completed, normal hexane is added, and red crystals, namely, the product 1-chlo-1-beta-phthalocyanine-5-phenanthroline ether-1-methylisopropyl benzene synthetic ruthenium (II) are separated out. The invention further discloses application of the phthalocyanine-aryl ruthenium compound.
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Paragraph 0037; 0038

(2017/05/27)

5,10,15,20-tetraphenylporphyrin diamine aryl ruthenium compound, and preparation method and purpose thereof
The invention discloses a 5,10,15,20-tetraphenylporphyrin diamine aryl ruthenium compound, and a preparation method and a purpose thereof. The 5,10,15,20-tetraphenylporphyrin diamine aryl ruthenium compound provided by the invention can be used for preparing medicine for treating oophoroma, and can be prepared into a form of an injection, a tablet, a pill, a capsule, a suspension or an emulsion to be used. The 5,10,15,20-tetraphenylporphyrin diamine aryl ruthenium compound provided by the invention has the advantages that the preparation method is simple; the raw materials can be easily obtained; the cost is low.
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Paragraph 0025-0028

(2017/08/29)

porphyrin aryl ruthenium complex as well as preparation method and use thereof
The invention discloses a porphyrin aryl ruthenium complex as well as a preparation method and use thereof. The porphyrin aryl ruthenium complex disclosed by the invention can be used for preparing a medicine for curing cancers, and can be prepared into injections, tablets, pills, capsules, suspension agents or emulsion agents for use. The porphyrin aryl ruthenium complex disclosed by the invention is simple in preparation method, the raw materials are easily obtained, and the preparation method has the advantage of low cost.
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Paragraph 0025; 0027; 0028

(2017/08/29)

A monofluoro-benzene ruthenium compound and its preparation and use
The present invention provides a fluorine benzene ruthenium compound and a preparation method and application thereof. The structure of the fluorine benzene ruthenium compound is shown in formula (I). The fluorine benzene ruthenium compound is synthesized and generated by dichloridized dichloro-2-methyl-isopropyl-benzo dirhodium and phenylacetyl diflunisal and shows a relatively strong inhibition activity on a human lymph cancer cell strain and a liver cancer strain of a human body. The fluorine benzene ruthenium compound can be used for preparing medicines for treating liver cancer and lymph cancer, and can be prepared to injections, tablets, pellets, capsules, suspensions or emulsions. The fluorine benzene ruthenium compound provided by the invention can improve the lipid solubility and the permeability of medicines, enhances the dissolubility of a biological film and prompts the speed of absorption and transmission in vivo, so that the physiological action changes.
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Paragraph 0025; 0029

(2017/12/28)

A method for improving the ability to resist infection of implant of the compound and its preparation and use (by machine translation)
The invention discloses a having the structural formula (I) used for improving the implant anti-infective compound of ability and its preparation and use. (I), its chemical name is a monochloro monocarbonyl chloride to the fluorinated benzene - 2 - compression N4 - Phenyl thiosemicarbazide methyl isopropyl the benzene gathers the ruthenium (II). On Staphylococcus aureus (ATCC 6538), Escherichia coli (ATCC 25922), white Candida albicans (ATCC 10231), bacillus subtilis (ATCC 9372) black variety has very strong bactericidal, has excellent antibacterial performance, but also to the osteoblast shown to promote the growth of bacteria, toxic, used for preparing the planting the performance of the and the prevention of implant related infection, has very obvious application potential. The present invention that the means for improving the ability to resist infection of dental implant is the preparation of the compounds of the method is simple, easily available raw materials, has the advantage of low cost. (by machine translation)
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Paragraph 0033; 0034; 0035; 0036-0040; 0045-0051; 0056-0062

(2017/08/25)

Tetraphenylporphyrin aryl ruthenium compound as well as preparation method and application thereof
The invention discloses a tetraphenylporphyrin aryl ruthenium compound as well as a preparation method and application thereof. The tetraphenylporphyrin aryl ruthenium compound disclosed by the invention can be used for preparing cancer treatment drugs and can be made into injection, tablets, pills, capsules, suspending agents or emulsion. The preparation method of the tetraphenylporphyrin aryl ruthenium compound disclosed by the invention is simple, the raw materials are easily available, and the cost is low.
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Paragraph 0025; 0026; 0027; 0028

(2017/08/29)

Tetraphenylporphyrin ether aryl ruthenium compound and preparation method and application thereof
The invention discloses a tetraphenylporphyrin ether aryl ruthenium compound and a preparation method and application thereof. The porphyrin-aryl ruthenium compound can be used in preparation of a medicine for treating cancers and can be made into an injection, tablets, pills, capsules, a suspending agent or an emulsion. The preparation method of the porphyrin-aryl ruthenium compound is simple; raw materials are easily available; and cost is low.
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Paragraph 0027; 0028

(2017/08/29)

For treating liver cancer of organic compounds and its preparation and use
The invention discloses an organic compound used for treating liver cancers as well as a preparation method and application thereof. The organic compound has a structural formula (III) in the specification. The chemical name of the organic compound is monochloro-thiophene-2-acetal N-phenyl thiosemicarbazide-methyl isopropylbenzene ruthenium monochloride (II). The organic compound shows good inhibitory activities towards gastric cancer SGC7901 cell lines and liver cancer BEL-7404 cell lines, can be used for preparing medicines for treating cancers, and can be used after being prepared into the forms, such as injections, tablets, pills, capsules, suspending agents or emulsion. The preparation method of the organic compound used for treating liver cancers is simple, is accessible in raw materials and has the advantage of low cost.
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Paragraph 0034; 0040; 0041

(2018/11/03)