- 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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- Synthesis, characterisation, crystal structures and biological studies of palladium(ii) complexes containing 5-(2-hydroxy-3-methoxy-phenyl)-2,4-dihydro[1,2,4]triazole-3-thione derivatives
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A series of new Pd(ii) complexes (1-4) were obtained from the reactions between K2[PdCl4], 3-methoxysalicylaldehyde-4(N)-substituted thiosemicarbazone [H2L1-H2L4] and 1,3-bis(diphenylphosphino)propane [dppp]. All the complexes were characterized by various spectroscopic techniques (IR, electronic, 1H-NMR and ESI-MS). The crystal structures of complexes 2 and 4 have been determined by single crystal X-ray diffraction. The binding affinity and binding mode of the palladium complexes (1-4) towards calf-thymus (CT) DNA and BSA (Bovine Serum Albumin) were studied by using UV-vis and fluorescence emission spectroscopy. These results showed that the binding of the complexes to DNA is through electrostatic interaction and the quenching of the complexes is static. Further they cleaved supercoiled DNA pBR322 without any added external agents. The alterations in the secondary structure of BSA by the Pd(ii) complexes were confirmed by synchronous and three dimensional fluorescence spectroscopy. The cytotoxicity of the complexes was evaluated by an MTT assay in the MCF-7 cell line and complex 3 exhibited significant activity (IC50 = 5.60 ± 0.04 μM), which was comparable with those of the other complexes. The morphological changes assessed by acridine orange and ethidium bromide staining revealed that the cell death occurred through apoptosis.
- Shanmugapriya,Dallemer,Prabhakaran
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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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- Triphenylene based metal-pyridine cages
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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.
- Berton, Giacomo,Lorenzetto, Tommaso,Borsato, Giuseppe,Sgarbossa, Paolo,Santo, Claudio,Visentin, Fabiano,Fabris, Fabrizio,Scarso, Alessandro
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supporting information
(2019/10/02)
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- Discrete Air-Stable Nickel(II)-Palladium(II) Complexes as Catalysts for Suzuki-Miyaura Reactions
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Four novel bidentate phosphine-Pd complexes coordinated by NiN2S2 metallodithiolate ligands were synthesized and characterized, including XRD analysis; these redox-active complexes are stable in air, and they survive column chromatography on silica gel. The Ni-Pd bimetallic complexes are demonstrated to be precatalyst for Suzuki-Miyaura cross-coupling reactions. The best of these has an overall yield of over 99% under only 1% catalyst loading. The role of NiN2S2 as a stabilizing bidentate ligand that is also oxidizable may account for its efficacy in the support of the catalysis.
- Zhao, Tiankun,Ghosh, Pokhraj,Martinez, Zachary,Liu, Xufeng,Meng, Xianggao,Darensbourg, Marcetta Y.
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supporting information
p. 1822 - 1827
(2017/05/15)
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- A double (mortars; concrete ; artificial stone) alkane dichloride method for the preparation of palladium complexes (by machine translation)
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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)
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Paragraph 0021; 0022; 0023; 0024; 0025
(2017/02/24)
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- Palladium-Catalyzed Aminomethylamination and Aromatization of Aminoalkenes with Aminals via C-N Bond Activation
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Thanks to the facile imine-enamine tautomerization, the β,γ-unsaturated hydrazones have been successfully utilized as surrogates of aminodienes for realizing the Pd-catalyzed tandem aminomethylamination/aromatization reaction with aminals via C-N bond activation. This direct and operationally simple protocol provides a fundamentally novel strategy to synthesize aromatic heterocycles from alkenes in the absence of external oxidant and base. Mechanistic studies suggested that aminal not only functioned as an aminomethyl source but also acted as formal oxidant and inner base to promote the aromatization.
- Li, Lixin,Liu, Peipei,Su, Yijin,Huang, Hanmin
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supporting information
p. 5736 - 5739
(2016/11/17)
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- Palladium-Catalyzed Formal Insertion of Carbenoids into Aminals via C-N Bond Activation
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A new strategy for selective insertion of metal carbenes into C-N bond has been developed via Pd-catalyzed C-N bond activation. A series of aminals and α-diazoesters with different substituents were successfully incorporated even in 0.1 mol % of catalyst under mild conditions, affording a wide range of α,β-diamino acid esters with quarternary carbon-centers. Preliminary mechanistic studies uncovered that the unique electrophilic cyclopalladated species could easily react with diazoacetates to generate a Pd-carbenoid intermediate which was involved in the catalytic cycle.
- Qin, Guiping,Li, Lixin,Li, Jiawen,Huang, Hanmin
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supporting information
p. 12490 - 12493
(2015/10/19)
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- Anion transport across phospholipid membranes mediated by a diphosphine-Pd(ii) complex
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The [Pd(dppp)(OTf)2] complex acts as an efficient transporter of halide anions, in particular the biologically relevant chloride anion, across a phospholipid bilayer. This journal is the Partner Organisations 2014.
- Milano, Domenico,Benedetti, Barnaba,Boccalon, Mariangela,Brugnara, Andrea,Iengo, Elisabetta,Tecilla, Paolo
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supporting information
p. 9157 - 9160
(2014/08/05)
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- Hydrogen-bonding-promoted oxidative addition and regioselective arylation of olefins with aryl chlorides
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The first, general, and highly efficient catalytic system that allows a wide range of activated and unactivated aryl chlorides to couple regioselectively with olefins has been developed. The Heck arylation reaction is likely to be controlled by the oxidative addition of ArCl to Pd(0). Hence, an electron-rich diphosphine, 4-MeO-dppp, was introduced to facilitate the catalysis. Solvent choice is critical, however; only sluggish arylation is observed in DMF or DMSO, whereas the reaction proceeds well in ethylene glycol at 0.1-1 mol % catalyst loadings, displaying excellent regioselectivity. Mechanistic evidence supports that the arylation is turnover-limited by the oxidative addition step and, most importantly, that the oxidative addition is accelerated by ethylene glycol, most likely via hydrogen bonding to the chloride at the transition state as shown by DFT calculations. Ethylene glycol thus plays a double role in the arylation, facilitating oxidative addition and promoting the subsequent dissociation of chloride from Pd(II) to give a cationic Pd(II)-olefin species, which is key to the regioselectivity observed.
- Ruan, Jiwu,Iggo, Jonathan A.,Berry, Neil G.,Xiao, Jianliang
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supporting information; scheme or table
p. 16689 - 16699
(2011/02/23)
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- Self-assembly and anion encapsulation properties of cavitand-based coordination cages
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Two novel classes of cavitand-based coordination cages 7a-j and 8a-d have been synthesized via self-assembly procedures. The main factors controlling cage self-assembly (CSA) have been identified in (i) a P-M-P angle close to 90° between the chelating ligand and the metal precursor, (ii) Pd and Pt as metal centers, (iii) a weakly coordinated counterion, and (iv) preorganization of the tetradentate cavitand ligand. Calorimetric measurements and dynamic 1H and 19F NMR experiments indicated that CSA is entropy driven. The temperature range of the equilibrium cage-oligomers is determined by the level of preorganization of the cavitand component. The crystal structure of cage 7d revealed the presence of a single triflate anion encapsulated. Guest competition experiments revealed that the encapsulation preference of cages 7b,d follows the order BF4- > CF3SO3- ? PF6- at 300 K. ES-MS experiments coupled to molecular modeling provided a rationale for the observed encapsulation selectivities. The basic selectivity pattern, which follows the solvation enthalpy of the guests, is altered by size and shape of the cavity, allowing the entrance of an ancillary solvent molecule only in the case of BF4-.
- Fochi,Jacopozzi,Wegelius,Rissanen,Cozzini,Marastoni,Fisicaro,Manini,Fokkens,Dalcanale
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p. 7539 - 7552
(2007/10/03)
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- Studies on palladium-bisphosphine catalyzed alternating copolymerization of CO and ethylene
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Palladium(II)-bisphosphine catalyzed copolymerization of CO and ethylene was studied in detail. The results showed that DPPPr/Pd(II) mole ratio, CF3COOH/Pd(II) mole ratio and solvent greatly influence the catalytic activity. Solvent effects were studied and in detail through end group analysis. With high pressure in situ 1H-NMR technique, the signals of coordinated ethylene at 4.4 ppm and methylene linked with Pd(II) (Pd - CH2-) at 0.6 ppm were observed. With high-pressure in situ IR technique three palladium carbonyl absorptions were observed generated at 1638 cm-1, 1616 cm-1 and 1970 cm-1, which may be assigned to three intermediates (3) (5) (6). With the above results, the copolymerization mechanisms were discussed. High-pressure in situ 31P-NMR experimental result showed that only mono- chelate ring complex (1) was produced when DPPPr/Pd(II) = 1; only bis-chelate ring complex (2) was produced when DPPPr/Pd(II) = 2; equimolar complex (1) and (2) were produced when DPPPr/Pd(II) = 1.5. Extended X-ray absorption fine structure (EXAFS) was used to calculate the coordination number (CN) and shell radius (R, in ?) of complexes (DPPPr)Pd(OCOCF3)2 (a), (DPPBu)Pd(OCOCF3)2 (b), (DPPEt)Pd(OCOCF3)2 (c), (DPPPr)2Pd(OCOCF3)2 (e), and two catalyst solutions of methanol freshly taken before and in the middle of copolymerization (named S1 and S2, respectively). The Pd - P bond length of complexes (a) (b) (c) are 2.25(3) ?, 2.33(3) ?, and 2.38(2) ?, respectively, Pd - O bond length of complexes (a) (b) (c) are 2.07(3) ?, 2.06(2) ? and 2.05(3) ?, respectively. In the order of complexes (a) (b) (c), the catalytic activity increases with Pd - P bond decreasing and Pd - O bond increasing, which may show that the chelate ring is more stable, the anions can go away more easily, and the corresponding catalyst is more efficient. The coordination number of two catalyst solutions S1 and S2 are increased by 1.9 and 0.9 compared with solid complex (a), which may show that 18-electron and five-coordinated pyramidal intermediates were produced and existed in the system besides 16-electron and four-coordinated square planar intermediates. (C) 2000 Elsevier Science B.V.
- Luo, He-Kuan,Kou, Yuan,Wang, Xi-Wen,Li, Da-Gang
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- Insertion of imines into palladium - acyl bonds: Towards metal-catalyzed alternating copolymerization of imines with carbon monoxide to form polypeptides
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From a methyl ligand, CO, and an imine a chelating amide ligand is formed by insertion of the C=N bond into the metal-acyl bond in cationic palladium(II) complexes (see reaction below). The cationic acylpalladium complexes are obtained from CO and readily accessible palladium starting materials. LL = diphosphane ligand.
- Kacker, Smita,Kim, Jang Sub,Sen, Ayusman
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p. 1251 - 1253
(2007/10/03)
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- Metal supported macrocycles : Synthesis and characterisation of some macrocycles derived from Ni(II), Pd(II) and Pt(II) and 1,3- and 1,4- bis(benzimidazole-l-yl-methylene)benzene ligands
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New macrocyclic squares of the type [(bisphos)M(BIX)]2 (BF)4.n CHCl3 where M=Ni(II), Pd(II) and Pt(II) have been synthesized using non-chelating ligands, viz., 1,3- and l,4-(benzimidazole-1-yl-methylene)benzene (hereafter 1,3- and 1,4-BIX) and [(bisphos)M(CH3OH)2(BF4)2] {for M=Ni(II) and Pd(II), bisphos- = diphenylphosphinopropane (dppp); for M = Pt(II), bisphos=diphenyl phosphinoethane (dppe)}. These complexes have been characterised using C, H, N analyses, IR, UV-VIS, 13C-NMR and FAB-mass studies. CPK model (Corey-Pauling-Koltun) of these macrocycles indicates that the cavity size is suitable for inclusion of benzene substituted guests.
- Chawla, Sukhvinder Kaur
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p. 904 - 907
(2007/10/03)
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- Reactivity of palladium(II) complexes with bidentate bis(phosphine) ligands toward the octahydrotriborate(1-) anion and dependence of the reaction upon halide arrangement: Molecular structure of the trans-(bis(diphenylphosphino)hexane)palladium(II) dichloride dimer
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The reactivity of the palladium(II) bis(phosphine) complexes, (Ph2P(CH2)nPPh2)PdCl2 (n = 1-6), toward the octahydrotriborate(1-) anion, [B3H8]-, has been investigated. For n = 1-4, the metallaborane (Ph2P(CH2)nPPh2)Pd(B 3H7) is produced, although the yield depends upon the organic chain length of the phosphino ligand and is maximized when n = 2. Our observation that no reaction occurs between the [B3H8]- anion and (bis(diphenylphosphino)pentane)- or (bis(diphenylphosphino)hexane)-palladium(II) dichloride leads us to examine the structure of these starting materials. Unlike (Ph2P(CH2)nPPh2)PdCl2 for n = 1-4, which are cis monomers, complexes with n = 5 or 6 are dimeric with a trans arrangement of chloro substituents; the molecular structure of trans-[(Ph2P(CH2)6PPh2)PdCl 2]2 is presented: triclinic, P1; a = 9.448 (2), b = 11.772 (2), c = 16.983 (3) ?; α = 74.18 (2), β = 87.14 (2), γ = 77.59 (2)°; V = 1774.9 (9) ?3, Z = 2; RF = 5.17%. A detailed comparison of this structure with those of related complexes is made.
- Housecroft, Catherine E.,Shaykh, Bilal A. M.,Rheingold, Arnold L.,Haggerty, Brian S.
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p. 125 - 130
(2008/10/08)
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- 31P and 13C solid-state NMR of tertiary phosphine-palladium complexes bound to silica
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Phosphorus-31 and carbon-13 NMR spectra with cross polarization and magic-angle spinning are used to characterize palladium-tertiary phosphine complexes and their precursors covalently bound to silica. Phosphorus-31 NMR is a good probe of complex formation and geometry, whereas 13C NMR is a good probe of ligand structure. The 36.44-MHz 31P spectrum of (≡SiOSiCH2CH2PPh2)2PdCl 2 shows two, barely resolved peaks at about 21 and 30 ppm assigned to the trans and cis complexes, respectively. These assignments are based on the chemical shifts of model compounds in both solution and the solid state. Uncomplexed phosphine and phosphine oxide are observed when complexes are prepared from phosphinated silica but not when the complexes are preformed and then attached to silica. The palladium dichloride complexes of bis(diphenylphosphino)methane, -ethane, and -propane, all of which have an approximately square-planar configuration, were examined as solid-state models for strained cis complexes on the silica surface. As in solution, the solid-state 31P chemical shifts of these compounds occur over a range of 127 ppm while the P-Pd-P angle varies from 73 to 91°. Hence, the 31P chemical shift is a very sensitive measure of strain in such complexes and confirms that the structures in solution are similar to those in the solid state. Applying these models, we find that the surface-bound complexes have mainly unstrained, trans configurations. Other species that have been examined on surfaces or as models include (dicyclohexylpropyl)phosphino complexes, for which cis and trans surface-bound complexes are observed, trimethylsilyl-capped samples, and phosphine oxides. Evidence is found for hydrogen bonding between bound phosphine oxide groups and silanol groups on the silica surface. Both the chemical shift anisotropy powder pattern and P-H cross-polarization rates indicate that the Pd-phosphine complex is rigidly bound to the silica surface.
- Komoroski, Richard A.,Magistro, Angelo J.,Nicholas, Paul P.
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p. 3917 - 3925
(2008/10/08)
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