- New Pd-Fe ferrocenyl antiparasitic compounds with bioactive 8-hydroxyquinoline ligands: a comparative study with their Pt-Fe analogues
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In the search for a more effective chemotherapy for the treatment of Human African Trypanosomiasis, a disease caused by the parasiteTrypanosoma brucei, the development of ferrocenyl compounds has arisen as a promising strategy. In this work, five new Pd-Fe heterobimetallic [PdII(L)(dppf)](PF6) compounds, including 8-hydroxyquinolyl derivatives HL1-HL5 as bioactive ligands and dppf = 1,1′-bis(diphenylphosphino)ferrocene as the organometallic co-ligand, were synthesized and fully characterized in the solid state and in solution. Molecular structures of three compounds were solved by single crystal X-ray diffraction methods. The compounds displayed submicromolar or micromolar IC50values against bloodstreamT. brucei(IC50: 0.33-1.2 μM), and good selectivity towards the pathogen (SI: 4-102) with respect to mammalian macrophages (cell line J774). The new Pd complexes proved to be 2-fold to 45-fold more potent than the drug nifurtimox but most of them are less active than their Pt analogues. Potential molecular targets were studied. The complexes interact with DNA but they do not alter the intracellular thiol-redox homeostasis of the parasite. In order to understand and predict the main structural determinants on the anti-T. bruceiactivity, a search of quantitative structure-activity relationships (QSAR) was performed including all the [M(L)(dppf)](PF6) complexes, where M = Pd(ii) or Pt(ii), currently and previously developed by us. The correlation obtained shows the relevance of the electronic effects, the lipophilicity and the type of metal. According to the QSAR study, compounds with electron-withdrawing ligands, higher lipophilicity and harboring Pt would result in higherT. bruceicytotoxicity. From the whole series of [M(L)(dppf)](PF6) compounds developed, where M = Pt(ii) or Pd(ii) and HL = 8-hydroxyquinolyl derivatives, Pt-dppf-L4 (IC50= 0.14 μM, SI = 48) was selected to perform an exploratory pre-clinical study in infected mice. This hit compound lacks acute toxicity when applied to animals in the dose/regimen described and exerts an anti-proliferative effect on parasites, which extends animal survival but is not curative.
- Rivas, Feriannys,Medeiros, Andrea,Quiroga, Cristina,Benítez, Diego,Comini, Marcelo,Rodríguez-Arce, Esteban,Machado, Ignacio,Cerecetto, Hugo,Gambino, Dinorah
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- Photo-oxidation of bis[1,2-bis(diphenylphosphino)ferrocene]-palladium(0) in CCl4 induced by ferrocene to solvent charge transfer excitation
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The electronic spectrum of Pd0[(PPh2C5H4)2Fen]2 in CCl4 shows an absorption at λmax = 338 nm that is assigned to a charge transfer-to-solvent (CTTS) transition from the ferrocene moiety to CCl4. The CTTS excitation leads to the formation of PdII[(PPh2C5H4)2Fe II]Cl2. It is suggested that the irradiation induces initially the generation of FeIII, which then oxidizes Pd0 by intramolecular electron transfer. Product formation takes place by a disproportionation of PdI.
- Kunkely, Horst,Vogler, Arnd
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- Stereospecific Synthesis of α- and β-C-Aryl-Δ2-Glycopyranosides from p-tert-Butylphenyl α-O-Δ2-Glycopyranoside via Grignard Reagents
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Palladium-catalysed coupling of p-tert-butylphenyl α-O-Δ2-glycopyranoside with various substituted arylmagnesium bromides provides the corresponding C-α-aryl-Δ2-glycopyranosides, while nickel-mediated reaction allows the preparation of the C-β-aryl anomers.
- Moineau, Christophe,Bolitt, Veronique,Sinou, Denis
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- Preparation, molecular structure, and solution properties of 1-[1,1′-bis(diphenylphosphino)ferrocene]palladatetraborane
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1-[1,1′-Bis(diphenylphosphino)ferrocene]palladatetraborane, 1-{(dppf)Pd}B3H7 (1), has been prepared by the reaction of (dppf)PdCl2 with octahydrotriborate(1-). The molecular structure of 1 has been determined: triclinic, P
- Housecroft, Catherine E.,Owen, Steven M.,Raithby, Paul R.,Shaykh, Bilal A. M.
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- The thiosulfate (S2O32?) ion; a neglected but simple hetero-donor ligand towards platinum(II), palladium(II) and nickel(II)
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Reactions of the thiosulfate ligand (as sodium thiosulfate, Na2S2O3·5H2O) with phosphine complexes of the group 10 metals Ni(II), Pd(II) and Pt(II) resulted in five neutral thiosulfate complexes, [Ni(S2O3)(dppe)] (dppe = Ph2PCH2CH2PPh2), [Pd(S2O3)(dppe)], [Pd(S2O3)(dppf)] (dppf = Fe(C5H4PPh2)2), [Pd(S2O3)(PPh3)2] and [Pt(S2O3)(PPh3)2]. X-ray structure determinations of [Pd(S2O3)(dppf)], [Pd(S2O3)(PPh3)2] and [Pt(S2O3)(PPh3)2] confirmed that thiosulfate ligand coordinates as a bidentate chelating ligand via both sulfur and oxygen donor atoms. In addition, reactions of the thiosulfate ligand with dinuclear chloride-bridged cyclopalladated complexes gave four mononuclear anionic complexes [Pd(S2O3)(damp)]? (damp = N,N-dimethylbenzylamino, (CH3)2NCH2C6H4), [Pd(S2O3)(ptpy)]? (ptpy = p-tolylpyridyl), ]Pd(S2O3)(bzpy)]? (bzpy = 2-benzylpyridyl) and [Pd(S2O3))pap)]? (pap = 2-(phenylazo)phenyl). The structure of (Ph3PCH2Ph)[Pd(S2O3)(pap)] by X-ray crystallography revealed the ability of thiosulfate ligand to cleave the bridging chloride ligand on the starting complexes by acting as an S,O-donor chelating ligand. An ESI mass spectrometric investigation showed that the coordinated thiosulfate ligand undergoes fragmentation at elevated capillary exit voltages.
- Henderson, William,Kaewthong, Aphiwat,Saunders, Graham C.
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- Meso -Tetra-(4-pyridyl)porphyrin/palladium(ii) complexes as anticancer agents
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This study reports the synthesis, structural characterization and cytotoxic activity of four new palladium/pyridylporphyrin complexes, with the general formula {TPyP[PdCl(P-P)]4}(PF6)4, where P-P is 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,2-bis(diphenylphosphino)butane (dppb) or 1,1′-bis(diphenylphosphino)ferrocene (dppf). The complexes were characterized by elemental analysis, and by FT-IR, UV/Vis, 1H and 31P{1H} NMR (1D/2D) spectroscopy. The slow evaporation of a methanolic solution of {TPyP[PdCl(dppb)]4}(PF6)4 (in an excess of NaBF4 salt) resulted in single crystals suitable for X ray diffraction, allowing the determination of the tridimensional structure of this complex, which crystallized in the P21/a space group. The cytotoxicity of the complexes against MDA-MB-231 (breast cancer cells) and MCF-10A (non-tumor breast cancer cells), was determined by the colorimetric MTT method, which revealed that all four complexes show selective indexes close to 1.2, lower than that of cisplatin for the same cells (12.12). The interaction of the complexes with CT-DNA was evaluated by UV-visible and viscosity measurements and it was determined that the complexes interact moderately with CT-DNA, probably by H-bonding/π-π stacking and electrostatic interactions. This journal is
- Alves, Kamilla M.,Ayalla, Alejando P.,Batista, Alzir A.,Dutra, Jocely De L.,Ellena, Javier,Gon?alves, Pablo J.,Guedes, Adriana P. M.,Honorato, Jo?o,Li?o, Luciano M.,Velozo-Sa, Vivianne S.
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p. 16254 - 16264
(2021/11/27)
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- Preparation method of [1, 1'-bis (diphenylphosphino) ferrocene] palladium dichloride
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The invention discloses a preparation method of [1, 1'-bis (diphenylphosphino) ferrocene] palladium dichloride, which comprises the following steps of: (a) adding palladium powder into an aqua regia solution, heating for dissolution, adding hydrochloric acid while the solution is hot to drive nitrate, cooling, and adding an ethanol-water mixed solution for dilution; (b) dissolving 1, 1'-bis (diphenylphosphino) ferrocene (dppf) in an organic solvent in a stirring state to obtain an organic solution of 1, 1'-bis (diphenylphosphino) ferrocene; and (c) dropwise adding the solution obtained in thestep (a) into the solution obtained in the step (b), stirring for reaction, cooling, filtering, washing, draining, and carrying out vacuum drying to obtain a red [1, 1'-bis (diphenylphosphino) ferrocene] palladium dichloride complex crystal. The initial raw material palladium powder is directly used for replacing palladium dichloride, the target product is directly synthesized, the synthesis period is shortened, the reaction steps are simplified, the efficiency is improved, the production cost is reduced, the yield of the target product is larger than 99%, and the purity of the target productis larger than 99%.
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Paragraph 0030-0048
(2021/02/06)
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- Preparation method of palladium complex
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The invention discloses a preparation method of a palladium complex. The method comprises the following steps: 1, dissolving palladium metal salt in diluted hydrochloric acid; 2, allowing a metal saltsolution obtained in the step 1 to pass through an anion exchange resin column to enable chloropalladate radicals to be exchanged onto resin; 3, enabling a diphenylphosphino ferrocene solution to flow through the resin to obtain red turbid liquid; and 4, carrying out filtering, and washing a precipitate with ethanol to separate the resin and the precipitate. The preparation method disclosed by the invention is simple to operate, capable of realizing continuous production, high in product purity, recyclable in reaction liquid and high in metal utilization rate.
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Paragraph 0025-0032
(2020/07/02)
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- Reactivity of hemilabile pyridyl- and methyl-substituted pyrimidylselenolates with [MCl2(dppf)] (M?=?Pd, pt; dppf?=?bis(diphenylphisphino)ferrocene)
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The bis(diphenylphisphino)ferrocene (dppf) derived palladium analogue of [PdCl2(dppf)] on reaction with the sodium salt of pyridyl/pyrimidyl selenolate yielded mononuclear cis configured complex [Pd(SeAr)2(dppf)] (Ar = C5H
- Chauhan, Rohit Singh,Cordes, David B.,Slawin, Alexandra M.Z.,Yadav, Seema,Dash, Chandrakanta
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supporting information
p. 125 - 129
(2018/04/17)
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- Oxidative Mechanochemistry: Direct, Room-Temperature, Solvent-Free Conversion of Palladium and Gold Metals into Soluble Salts and Coordination Complexes
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Noble metals are valued, critical elements whose chemical activation or recycling is challenging, and traditionally requires high temperatures, strong acids or bases, or aggressive complexation agents. By using elementary palladium and gold, demonstrated here is the use of mechanochemistry for noble-metal activation and recycling by mild, clean, solvent-free, and room-temperature chemistry. The process leads to direct, efficient, one-pot conversion of the metals, including spent catalysts, into either simple water-soluble salts or metal–organic catalysts.
- Do, Jean-Louis,Tan, Davin,Fri??i?, Tomislav
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p. 2667 - 2671
(2018/02/06)
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- Mixed ligand, palladium(II) and platinum(II) complexes of tertiary diphosphineswithS-1H benzo[d] imidazole-2-yl benzothioate
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Palladium(II) and platinum(II) complexes containing the mixed ligands tertiary diphosphinesdppm. dppp and dppf with Thioester ligand S-1H benzo[d] imidazole-2-yl benzothioate (HSBIBT) have been prepared by the reaction of PdCl2 and PtCl2/
- Ali, Karwan Omer,Mohammad, Hikmat Ali,Gerber, Thomas,Hosten, Eric
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p. 584 - 592
(2017/05/26)
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- Aromatic amine N-oxide organometallic compounds: Searching for prospective agents against infectious diseases
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In search of prospective agents against infectious diseases, 1,1′-bis(diphenylphosphino)ferrocene pyridine-2-thiolato-1-oxide M(II) hexafluorophosphate compounds [M(mpo)(dppf)](PF6), where M = palladium or platinum, were synthesized and fully characterized in the solid state and in solution using experimental and DFT computational techniques. The compounds are isomorphous and the M(II) transition metal ions are in a nearly planar trapezoidal cis-coordination bound to the pyridine-2-thiolato-1-oxide (mpo) and to the 1,1′-bis(diphenylphosphino)ferrocene molecules, both acting as bidentate ligands. Both compounds showed high cytotoxic activity on Trypanosoma cruzi and Mycobacterium tuberculosis (MTB) and acceptable selectivities towards MTB, but good to excellent selectivity index values as anti-T. cruzi compounds. The inclusion of the ferrocene moiety (dppf ligand) improved the selectivity towards the parasite when compared to the previously reported [M(mpo)2] complexes. Related to the probable mechanism of action of the complexes, molecular docking studies on modelled T. cruzi NADH-fumarate reductase (TcFR) predicted that both be very good inhibitors of the enzyme. The effect of the compounds on the enzyme activity was experimentally confirmed using T. cruzi protein extracts. According to all obtained results, both [M(mpo)(dppf)](PF6) compounds could be considered prospective anti-trypanosomal agents that deserve further research.
- Rodrguez Arce, Esteban,Mosquillo, M. Florencia,Prez-Daz, Leticia,Echeverra, Gustavo A.,Piro, Oscar E.,Merlino, Alicia,Coitio, E. Laura,Marngolo Ribeiro, Camila,Leite, Clarice Q. F.,Pavan, Fernando R.,Otero, Luca,Gambino, Dinorah
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p. 14453 - 14464
(2015/08/24)
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- Antibacterial piperidinyl substituted 3,4-dihydro-1H-[1,8]naphthyridinones
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The present invention is related to novel compounds of formula (I) that inhibit the activity of the Fab1 enzyme which are therefore useful in the treatment of bacterial infections. It further relates to pharmaceutical compositions comprising these compounds, and chemical processes for preparing these compounds.
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Page/Page column
(2014/06/24)
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- New acetonyl palladium(II) complexes
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[Pd(CH2C(O)Me)Cl]n (1), reacts with P- and N-donor ligands to afford cis-[Pd{CH2C(O)Me}Cl(dppf)] (dppf = bis(diphenylphosphino)ferrocene (2)) and [Pd(CH2C(O)Me)ClL 2] (L = pyridine = py (3), 4-Me-pyri
- Vicente, Jose,Arcas, Aurelia,Fernandez-Hernandez, Jesus M.,Bautista, Delia
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p. 3978 - 3985
(2009/02/05)
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- METAL COMPOUND AND PREPARATION METHOD THEREFOR
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The invention concerns the preparation of a metal chelate, in particular a precious metal β-diketonate or a precious metal phosphine complex MLaXb, where M is a metal atom, L is a ligand, X is an anion which is preferably a halide, HCO3ˉ, NO3ˉ, CO32é or carboxylate, a is a number equal to or less than the coordination number of the metal, b is 0, 1, 2 or 3, comprising reacting an ammine compound of metal M with a complexing compound, which is preferably a phosphine or a diketonate. Metal compounds which can be made by this process are also described.
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Page/Page column 6
(2010/11/26)
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- Palladium complexes with metallocene-bridged bidentate diphosphine ligands: Synthesis, structure, and catalytic activity in amination and cross-coupling reactions
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The syntheses and characterization of series of new metallocene-bridged diphosphines and the structures of complexes of some of them with Pd(II) are reported. These complexes were examined as the catalysts in amination reactions of halogenoarenes and in the Suzuki reaction. The complexes based on ruthenocene (2) and osmocene (3) showed lower activities then the palladium complex with dppf in amination reactions and the same activities in the Suzuki reaction. New palladium complexes with the bidentate bulky and electron-rich ligands Fe(η5-C5H4P(o-PriC 6H4)2)2 (6) and Feη5- C5H4P(o-MeOC6H4)2) 2 (5) showed a very high catalytic activity in amination and Suzuki coupling of aryl bromides. A complex with ligand 6 was used in the amination of 4-bromotoluene by primary and secondary amines and showed excellent activity.
- Gusev, Oleg V.,Peganova, Tat'yana A.,Kalsin, Alexander M.,Vologdin, Nikolai V.,Petrovskii, Pavel V.,Lyssenko, Konstantin A.,Tsvetkov, Aleksey V.,Beletskaya, Irina P.
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p. 2750 - 2760
(2008/10/09)
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- Carboxylation of (DPPF)-MCl2 [DPPF=1,1′- bis(diphenylphosphino)ferrocene; M=Pt or Pd] in aqueous and non-aqueous solutionCrystal and molecular structures of [Pt(C2O4)(DPPF)] and of [PtCl(NO3)(DPPF)]
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Treatment of the complexes [MCl2(DPPF)] (M=Pt or Pd) {readily prepared in high yield from [MCl2(DMSO)2] (M=Pt (cis-) or Pd (trans-) and DPPF in CHCl3} with two molar proportions of AgNO3 in H2/s
- Al-Allaf, Talal A.K.,Schmidt, Harry,Merzweiler, Kurt,Wagner, Christoph,Steinborn, Dirk
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- Reaction of Palladium and Platinum Complexes Bearing α,/β-Unsaturated Carbonyl Compounds with Carbon Electrophiles: Control over Site of Electrophilic Attack, Oxygen or Metal
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The reaction of (η2-CH2=CHCHO)ML2 (M = Pd, Pt; L = PPh3, L2 = DPPF) with methyl triflate gave η3-methoxyallyl complexes [(η3-CH 3OCHCHCH2)ML2][OTf]. X-ray diffraction analysis on [(η3-CH3OCHCHCH2)M(dppf)] [OTf] (M = Pd, Pt) showed a distorted η3-allyl structure. The enone complexes (η2-CH2=CHCOCH3)M(PPh 3)2 also reacted with methyl triflate to give [(η 3-CH3OC(CH3)CHCH2)M(PPh 3)2] [OTf]. It was proposed that these complexes were formed by the direct electrophilic attack of methyl triflate at the carbonyl oxygen of the enal or enone ligand on the palladium and platinum. In fact, no insertion of acrolein into the platinum-methyl bond of the separately isolated methylplatinum complex proceeded. On the other hand, methyl iodide underwent oxidative addition with zerovalent enal or enone complexes to give methylmetal complexes concomitant with dissociation of an enal or enone molecule.
- Morita, Masaki,Inoue, Katsuharu,Ogoshi, Sensuke,Kurosawa, Hideo
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p. 5468 - 5472
(2008/10/09)
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- Isolation and structural characterization of some stable Pd(II) carboxylate complexes supported by 1,1′-bis(diphenylphosphino) ferrocene (dppf)
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Although catalytically active palladium phosphine carboxylates are generally unstable, a series of such complexes are stabilized by dppf, viz. Pd(O2CR)2(dppf) [R = CF3I, CF2CF3 II [1,43] CF2/sub
- Neo, Yew Chin,Yeo, Jeremy Shu Lip,Low, Pauline Meng Neo,Chien, Sheau Wei,Mak, Thomas C.W,Vittal, Jagadese J,Hor, T.S.Andy
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p. 159 - 168
(2007/10/03)
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- Synthesis, X-ray, spectroscopic and a preliminary Suzuki coupling screening studies of a complete series of dppfMX2 (M=Pt, Pd; X=Cl, Br, I)
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A complete series of dppfMX2 (M=Pt, Pd; X=Cl, Br, I) compounds have been synthesized using different routes, and characterized fully. The synthesis of dppfPdI2 has been achieved by reacting Pd(COD)Cl2 with dppf in the presence of NaI. X-ray structures of dppfPdBr2 and dppfPdI2 have also been reported for the first time in this study. A preliminary Suzuki coupling screening study reveals that dppfPdX2 compounds are superior to the conventional Ph3P-based catalysts and bidentate phosphine-based ligands. Reactions carried out under in situ conditions also gave a similar trend, but their respective activities were much lower than that of the fully formed catalysts.
- Colacot, Thomas J.,Qian, Hu,Cea-Olivares, Raymundo,Hernandez-Ortega, Simon
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p. 691 - 697
(2007/10/03)
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- Substituted Metal Carbonyls. Part 21. as a Metalloligand in Heteropolymetallic Aggregates of AuI, PdII and PtII. Crystal and Molecular Structures of 2> and
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The complexes behave like a monodentate phosphine ligand and displace the labile ligands from , trans- and cis- (dmso = dimethyl sulfoxide) to yield the corresponding dppf-bridged heteropolymetallic complexes of general formula xy> (M' = Au, x = y = 1; M' = Pd or Pt, x = y = 2).Only the trans isomers have been isolated for PdII and PtII.Isomerisation of the M' = Pt, M = Cr complex to the cis form, followed by partial elimination of to form , after 3d in CDCl3 was revealed by NMR spectroscopy.The solution characteristics of both geometrical isomers of the representative M' = Pt, M = Cr complex have been established by two-dimensional NMR studies.UV-Photolytic degradation of the M' = Pd or Pt, M complexes generally gave , , and .The molecular structures of trans-2> and have been determined.The former represents a trimetallic pentanuclear aggregate and the latter a metalloligand with a pendant phosphine on a bimetallic complex.Cyclic voltammetry of all the complexes has been examined and generally reveals one chemically reversible phosphinoferrocene-based oxidation, followed by an irreversible oxidation of the complex.
- Phang, Lai-Tee,Au-Yeung, Steve C. F.,Hor, T. S. Andy,Khoo, Soo Beng,Zhou, Zhong-Yuan,Mak, Thomas C. W.
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p. 165 - 172
(2007/10/02)
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- Anxiolytic 4-aminoquinoline-3-carboxamides
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The present invention comprises certain amide derivatives of 4,8-disubstituted quinoline-3-carboxylic acids of formula I; pharmaceutically acceptable salts of the compounds of formula I; pharmaceutical compositions containing a compound of formula I, or a pharmaceutically acceptable salt thereof, for use in the treatment of anxiety; and processes for the manufacture of the compounds of formula I, as well as intermediates for use in such manufacture.
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- Dichloropalladium(II): An Effective Catalyst for Cross-Coupling of secondary and Primary Alkyl Grignard and Alkylzinc Reagents with Organic Halides
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Several phosphine-palladium and -nickel complexes were examined for their catalytic activity in the reaction of sec-butylmagnesium chloride with bromobenzene, (E)-β-bromostyrene, 4-bromoanisole, and 2-bromotoluene.Dichloropalladium(II) was found to be by far the most active and selective catalyst to give the corresponding sec-butyl derivatives in high yields with no byproducts.The palladium-dppf complex was also found highly effective in catalyzing the reaction of n-butylmagnesium chloride and sec- and n- butylzinc chloride with organic bromides to give the corresponding cross-coupling products in high yields.The structure of PdCl2(dppf) has been determined by an X-ray diffraction study.It is proposed that the high efficiency of PdCl2(dppf) catalyst can be ascribed to its large P-Pd-P angle and small Cl-Pd-Cl angle.
- Hayashi, Tamio,Konishi, Mitsuo,Kobori, Yuji,Kumada, Makoto,Higuchi, Taiichi,Hirotsu, Ken
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p. 158 - 163
(2007/10/02)
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