19978-61-1Relevant articles and documents
Structurally different mono-, bi- and trinuclear Pd(II) complexes and their DNA/protein interaction, DNA cleavage, and anti-oxidant, anti-microbial and cytotoxic studies
Shanmugapriya,Jain, Ruchi,Sabarinathan,Kalaiarasi,Dallemer,Prabhakaran
, p. 10324 - 10338 (2017)
A series of new structurally different Pd(ii) complexes was obtained by the reactions between K2[PdCl4], 3-methoxysalicylaldehyde-4(N)-substituted thiosemicarbazone [H2L1-H2L4] and bis(diphenylphosphino)ethane [dppe]. All the complexes were characterized by using various spectral techniques (IR, electronic, 1H-NMR and mass spectroscopy). The crystal structures of complexes 1, 3, 4 and 3a & 4a were determined using X-ray crystallographic technique. The interactions of the new complexes with calf thymus DNA (CT-DNA) and bovine serum albumin (BSA) were evaluated using various spectroscopic methods, which showed the interaction potential of the complexes with CT-DNA and BSA. Further, they cleaved supercoiled DNA pBR322. The anti-oxidant profiles of the complexes were found to be better than the standards against 2,2′-diphenyl-1-picrylhydrazyl radicals (DPPH) and superoxide anion radicals. The antibacterial activity of the complexes against five pathogenic bacteria such as Staphylococcus aureus, Salmonella typhi, Escherichia coli, Bacillus subtilis and Pseudomonas aeruginosa was found to be better than their parent ligands. The complexes exhibited potential cytotoxicity against human breast cancer cells (MCF-7) in the following order: 4 > 3 > 1 > cisplatin > 2.
New alkoxycarbonyl complexes of palladium (II) and their role in carbonylation reactions carried out in the presence of an alkanol
Bertani, R.,Cavinato, G.,Toniolo, L.,Vasapollo, G.
, p. 165 - 176 (1993)
The new complexes of general formula trans-Pd(COOR)ClL2 =PPH3 R=Et, n-Pr, iso-Pr, n-Bu, iso-Bu, 2-ethoxyethyl, cyclopentyl, cyclohexyl; L=1,2-diphenylphosphinoethane, R=Et) are prepared reacting trans -PdCl2L2, suspended in an alkanol, under 10-50 atm of carbon monoxide, at 50-70°C, in presence of a base such as a trialkylamine or a carboxylic acid anion. They have been characterized by IR, 1H and 31P NMR spectroscopy. The complexes with R=Me and Et show two absorption bands centered at ca. 1650 cm-1, which are probably due to conformational isomers with cis and trans geometry. The other show only one band at ca. 1650 cm-1. The 1H NMR and 31P NMR spectra of all the monophosphine complexes show that only one isomer is present in solution. Instead, for the diphosphine ethoxycarbonyl complex the 1H NMR spectra suggest that two isomers are present, in the ratio of ca. 1:1, as confirmed by decoupling experiments. The two isomers may take origin from different orientation of the alkoxycarbonyl ligand with respect to the asymmetrical metal centre, because of hindered rotation around the Pd-C bond due to the partial double bond character. The R group of the alkoxycarbonyl ligand can be exchanged with a different R' group by reacting the Pd(COOR)Cl(PPh3)2 complex with an excess of R'OH. The reaction is practically quantitative when R is bulkier than R'. The alkoxycarbonyl complexes react with the corresponding alkanol, in the presence of a base such as a trialkylamine, at 90-100°C, under carbon monoxide, yielding Pd(0) carbonyl-phosphine complexes with formation of dimethyl carbonate in an almost quantitative yield. They react also with water giving off CO2 and yielding Pd(0) complexes. The reaction is promoted by an acid of a noncoordinating anion such as HBF4. Instead, the reaction with HCl yields the corresponding dichloride of Pd(II), beside carbon monoxide and the corresponding alkanol. The role of these complexes in catalytic alkoxycarbonylation reactions is discussed.
PREPARATION AND REACTIONS OF HYDROXO-ENYLPALLADIUM(II) DERIVATIVES
Rotondo, Enrico,Priolo, Francesca Cusmano,Donato, Andrea,Pietropaolo, Rosario
, p. 273 - 280 (1983)
Some new hydroxo-enyl derivatives of palladium(II) of the type 2, and PF6 (C7H8 = norbornadiene, diene = norbornadiene or 1,5-cyclooctadiene; L-L = 2,2'-dipyridyl or 1,10-phenanthroline) have been made by nucleophilic attack of H2O on the diene coordinated to the metal in dispositively charged complexes.Evidence is presented to show that the hydroxonorbornenyl-1,2-bis(diphenylphosphino)ethane palladium(II) is involved as an intermediate, in an unusual example of oxidation of the alcoholic group through a palladium(II)-mediated intramolecular hydrogen transfer.
ELECTROPHILIC ATTACK ON (2-NORBORNANONE)PALLADIUM(II) DICHLORIDE
Rotondo, E.,Cusmano, F. Priolo,Neri, G,Donato, A.,Pietropaolo, R.
, p. 429 - 436 (1985)
The protonolysis of the complex (2-norbornanone)palladium(II) chloride(I) has been studied.Comparison of the 13C NMR spectra of samples of 2-norbornanone obtained by treatment with HCl or DCl, unambiguously reveals that the carbon of the ketone was previously coordinated to the palladium(II).Kinetic results for the electrophilic cleavage of I are also reported.The rate law and the deuterium isotope effect suggest a rate-determining proton transfer to the palladium-carbon ?-bond, which takes place through a symmetrical three-centre transition state.
The coordination chemistry of sulfonyl-substituted thioureas towards the d8 metal centres platinum(II), palladium(II), nickel(II) and gold(III)
Henderson, William,Risi, Matthew C.,Saunders, Graham C.
, (2021/07/13)
Reactions of the complexes cis-[PtCl2(PPh3)2], [PtCl2(dppp)] (dppp = Ph2P(CH2)3PPh2), [MCl2(dppe)] (dppe = Ph2P(CH2)2PPh2, M = Ni, Pd), [PdCl2(bipy)] (bipy = 2,2′-bipyridine) and [AuCl2(bp)] (bp = cyclometallated 2-benzylpyridine) with p-TolSO2NHC(S)NHPh and Et3N in refluxing methanol gave a series of new thiourea complexes containing the ligand bound as a dianion through the S and the NPh groups. The related thioureas RSO2NHC(S)NHPh (R = Me, Et) and p-TolSO2NHC(S)NHCH2CH=CH2 were also reacted with cis-[PtCl2(PPh3)2] to form the corresponding complexes [Pt{RSO2NC(S)NPh}(PPh3)2] and [Pt{TolSO2NC(S)NCH2CH=CH2}(PPh3)2] respectively. X-ray structure determinations were carried out on the thiourea MeSO2NHC(S)NHPh and its platinum complex [Pt{MeSO2NC(S)NPh}(PPh3)2], as well as [Pt{TolSO2NC(S)NPh}(PPh3)2]. Both complexes form the distal isomer with a remote NSO2R group, and no evidence was observed for isomerisation of these platinum complexes in solution. The palladium complexes [Pd{TolSO2NC(S)NPh}L2] [L2 = Ph2PCH2CH2PPh2 (dppe), or 2,2′-bipyridine (bipy)] undergo decomposition in solution to form the sulfide-bridged aggregates [Pd3S2(L2)3]2+, identified by ESI MS and 31P NMR.
Meso -Tetra-(4-pyridyl)porphyrin/palladium(ii) complexes as anticancer agents
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.
, p. 16254 - 16264 (2021/11/27)
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
Pyrrole thioamide complexes of the d8 metals platinum(II), palladium(II) and gold(III)
Tang, Haiming,Saunders, Graham C.,Ma, Xiaochuan,Henderson, William
, (2019/12/09)
Reactions of the cycloaurated gold(III) complexes [AuCl2(2-benzylpyridyl)] and [AuCl2(C6H4CH2NMe2)] with a set of pyrrole-2-thioamide ligands, containing various substituents on the pyrrole ring, gave a series of new gold(III) pyrrole thioamide complexes. X-ray crystal structures on two complexes indicate that the pyrrole thioamide ligand is coordinated through the deprotonated pyrrole nitrogen, as well as the sulfur atom of the deprotonated thioamide group, forming five-membered chelate ring complexes. In both complexes, the two highest trans-influence donor atoms (C and S) are mutually cis. Related sets of platinum(II) and palladium(II) pyrrole thioamide complexes were similarly prepared by reactions of cis-[PtCl2(PPh3)2] and [PdCl2(dppe)] (dppe = Ph2PCH2CH2PPh2)] respectively. The complexes were characterised by NMR and IR spectroscopies, and ESI mass spectrometry. A preliminary investigation of the activity of a selection of compounds towards A549 (adenocarcinomic human alveolar basal epithelial) cells was also carried out.
A group of diphosphine-thiosemicarbazone complexes of palladium: Efficient precursors for catalytic C–C and C–N coupling reactions
Thapa, Kiran,Paul, Piyali,Bhattacharya, Samaresh
, p. 232 - 239 (2018/11/06)
Reaction of 4-R-benzaldehyde thiosemicarbazone (denoted in general as HL-R; where H stands for the dissociable acidic proton and R (R = OCH3, CH3, H, Cl and NO2) for the substituent) with [Pd(dppe)(EtOH)2]2+, generated in situ via interaction of [Pd(dppe)Cl2] (dppe = 1,2-bis(diphenylphosphino)ethane) with AgNO3 in hot ethanol, in the presence of triethylamine affords a group of orange complexes of the type [Pd(dppe)(L-R)]NO3. Structures of [Pd(dppe)Cl2] and [Pd(dppe)(L-OCH3)]NO3 have been determined by X-ray crystallography. In the [Pd(dppe)(L-R)]NO3 complexes, the thiosemicarbazone ligands are coordinated to the metal center as monoanionic bidentate N,S-donors forming five-membered chelate rings. The [Pd(dppe)(L-R)]NO3 complexes show intense absorptions in the visible and ultraviolet regions, which have been analyzed by TDDFT calculations. All the [Pd(dppe)(L-R)]NO3 complexes are found to efficiently catalyze Suzuki-type C–C and Buchwald-type C–N coupling reactions.
Triphenylene based metal-pyridine cages
Berton, Giacomo,Lorenzetto, Tommaso,Borsato, Giuseppe,Sgarbossa, Paolo,Santo, Claudio,Visentin, Fabiano,Fabris, Fabrizio,Scarso, Alessandro
supporting information, (2019/10/02)
C3-symmetric pyridine containing tris-benzyl-O-substituted hexahydroxytriphenylene derivatives were prepared and used in combination with square-planar Pd(II) and Pt(II) complexes for the self-assembly of molecular cages in solution. The formation of a trigonal bipyramid M3L2 cage was demonstrated by multinuclear NMR analyses and pseudo 2D DOSY experiments and supported by semi-empirical calculations.
A double (mortars; concrete ; artificial stone) alkane dichloride method for the preparation of palladium complexes (by machine translation)
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Paragraph 0015; 0016; 0017; 0018; 0019, (2017/02/24)
The invention discloses a double (mortars; concrete ; artificial stone) alkane second palladium chloride complex preparation method, the method is:a, preparation chlorine arrowhead acid solution; b, the double (mortars; concrete ; artificial stone) alkane adding N, N-dimethyl formamide (mortars; concrete ; artificial stone) is made of the alkane-N, N-dimethyl formamide solution; three, under stirring condition to the double (mortars; concrete ; artificial stone) N of paraffins, N-dimethyl formamide solution adds by drops the chlorine arrowhead acid solution, stirring reaction after the completion of the dropping, cooling after-filtration, the filter cake obtained; four, washing the filter cake, the filter cake after washing is then subjected to vacuum drying, to get double (mortars; concrete ; artificial stone) alkane second palladium chloride complex. The invention directly the palladium source is palladium sponge, to double with the ligand chlorine arrowhead acid (mortars; concrete ; artificial stone) alkane in the solvent DMF in one-step synthesis target product, omits the intermediate palladium chloride, palladium chloride process for the preparation of acetonitrile, has the advantages of simple technique, cycle is short, low cost, and the like. (by machine translation)
