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Three dinuclear palladium(II) complexes with 2,2?-bipyridine (bpy) were synthesized from [Pd(bpy)Cl2] and 3-aminopropanethiol (Hapt) by changing reaction conditions. It was found that Hapt can adopt three different coordination modes (Hapt-kappa2S, apt-kappaN,kappa2S, H-1apt-kappa2N,kappa2S) dependent on its protonation states in this coordination system.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Oxidative addition of donor-functionalised 4-iodoimidazolium salts to palladium(0) provides a selective route for the preparation of abnormal chelating N-heterocyclic carbene complexes and enables the introduction of a variety of donor groups. The activation of the C4 position does not necessitate protection of the imidazolium C2 position, thereby leaving this site available for further modification. While metallation of the unsubstituted C2 position of the N-heterocyclic carbene ligand was unsuccessful when palladium was bound to the C4 carbon atom, sequential metallation of first the C2 position, by means of transmetallation, followed by C4-I oxidative addition, afforded a dimetallic complex comprised of two palladium centres bridged by a single NHC ligand. Oxidative addition of 4-iodoimidazolium salts to low-valent palladium(0) provides access to abnormal NHC-palladium complexes without requiring protection of the C2 position. Hence, this site is available for further functionalisation which allows, for example, dimetallic complexes to be prepared.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Lanthanide(III) coordination compounds are employed in several fundamental and applied research fields such as organic synthesis, bioinorganic chemistry, optical and magnetic imaging, catalysis, environment and geochemistry. All these applications have been favoured by the recent developments of a detailed knowledge of fundamental properties (electronic, spectroscopic, thermodynamic, magnetic, structural) of elements, ions and their compounds.Ln3+ are hard acids and present strong affinity for charged ligands or neutral O- and N-donors, as indicated by a wide number of papers concerning formation of their complexes in solution. These studies allowed one to gain information on the complex stabilities, the metal-ion selectivity of a given ligand, the influence of the solvent on the nature and stability of the species in solution. Most of the above studies deal with aqueous solutions, while studies in non-aqueous media are less common. Despite more limited, investigations in aprotic solvents are particularly interesting as they allow one to extend the knowledge on the coordination chemistry of lanthanide(III), disclosing metal-ligand interactions not easily accessible in water due to ligand protonation equilibria, Ln(III) hydrolysis and strong hydration of the cations, which hampers interactions with neutral donors.This review analyzes a wide number of thermodynamic studies concerning formation of lanthanide(III) complexes with selected, simple neutral N-donors (amines, pyridines), O-donors (crown ethers, aza-crown ethers and cryptands) and charged inorganic ligands (halides, thiocyanate, nitrate, perchlorate, triflate) in non-aqueous solvents. The main aim of the review is to face the basic question of what are the factors governing the complex stability and selectivity within the lanthanide series and how are they influenced by different coordinating media. Fundamental properties of Ln ions, such as ionic radii, common oxidation states and structural aspects of their solvates are as well analyzed.Several points emerged from a critical analysis of the papers reviewed:. i)Ln3+ salts used in thermodynamic studies in poor coordinating solvents are often not completely dissociated and, in this case, the data obtained reflect multiple simultaneous equilibria in solution. Comparisons between thermodynamic results in poor and high solvating media must be therefore regarded with caution as they may refer to different reacting metal-species, hence, to different metal-ligand equilibria.ii)High solvating aprotic media can be considered as ideal for thermodynamic studies since lanthanide(III) is only present as Ln(solv)n3+species. However, in this case, the strong solvation of Ln3+ ions hinders complex formations with weak or relatively weak donors.iii)Solvation of lanthanide(III) cations in non-aqueous solutions is generally a major factor in determining the complex stabilities which, for the different kinds of ligands examined, follow the general trend: PC>AN>MeOH>DMF>DMSO.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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A neutral hexacoordinate silicon complex containing two 2,6-bis(benzimidazol-2?-yl)pyridine (bzimpy) ligands has been synthesized and explored as a potential electron transport layer and electroluminescent layer in organic electronic devices. The air and water stable complex is fluorescent in solution with a lambdamax = 510 nm and a QY = 57%. Thin films grown via thermal evaporation also fluoresce and possess an average electron mobility of 6.3 × 10-5 cm2 V-1 s-1. An ITO/Si(bzimpy)2/Al device exhibits electroluminescence with lambdamax = 560 nm.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data. COA of Formula: C10H8Cl2N2Pd, If a proposed mechanism predicts the wrong experimental rate law, however, the mechanism must be incorrect.Welcome to check out more blogs about 14871-92-2, in my other articles.

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Abstract: A series of bipyridyl (Bpy) Pd(II) complexes with 3-hydroxyflavone (Fla) [PdBpyFlaR][BF4] (R=OCH3 (1), R=CH3 (2), R=H (3), R=Cl (4)) were prepared and characterized. The molecular structures of the four compounds were determined by UV?Vis, 1H NMR, 13C NMR, COSY, HSQC, HMBC, FTIR, ESI mass spectra and elemental analysis. Their ability to release carbon monoxide was investigated through oxygenation reaction under various conditions of temperature and light irradiation. The nitroxygenation reaction was also studied with nitroxyl, HNO, generated in situ from Angeli?s salt. The experimental results showed that oxygenation reaction of [PdBpyFla]+ with oxygen happens at high temperature (> 80 C) and light does not affect the reaction, whereas nitroxygenation reaction with HNO happens at room temperature without light irradiation. Carbon monoxide released from the complexes during the nitroxygenation reaction was trapped by deoxymyoglobin. Graphic abstract: [Figure not available: see fulltext.]

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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The design of molecule-based systems displaying tuneable optical and/or magnetic properties under external stimuli has received a great deal of attention in the past few years. This interest is driven by the potential applications in high-performance molecule-based electronics in the areas of recording media, switches, sensors, and displays. As an example, three-dimensional Fe/Co Prussian blue compounds exhibit a concomitant change in magnetic and optical properties due to a temperature- or light-induced metal-to-metal electron transfer. The foregoing remarkable properties in Prussian blues prompted us to design soluble molecular fragments of these coordination networks through a rational building-block approach in order to mimic their properties on a single molecule. With a judicious choice of the ligands for the iron and cobalt molecular precursors, we prepared a dinuclear cyanido-bridged Fe/Co complex that exhibits an unexpected temperature-dependent spin crossover in the solid state while an intramolecular electron transfer triggered by protonation is observed in solution.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

09/22/21 News Some scientific research about 14871-92-2

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The new gold(III), palladium(II), and platinum(II) complexes with 3-((4-nitrophenyl)thio)phenylcyanamide (HL) and 2,2?-bipyridine (bpy) ligands of formula [M(bpy)LCl] (M = Pd(II),1, Pt(II), 2) or [Au(bpy)LCl]Cl, 3, have been synthesized and fully characterized. The cytotoxicity of free ligands and complexes 1?3 were evaluated against HT-29 (colorectal adenocarcinoma), MCF-7 (breast), and HeLa (human squamous cervical adenocarcinoma) cancer cell lines along with MRC-5 non-tumorigenic cells (human lung fibroblasts) and their activity has been compared to the familiar platinum-based anticancer agent cisplatin. The free ligands bpy and HL were ineffective against the cancer cell lines. However, the complexes 1?3 showed a significant in vitro antitumor activity with IC50 values in the low micromolar. The complexes 1?3 were revealed to produce cellular reactive oxygen species (ROS). The most potent ROS producer, complex 3, also elicited the highest cytotoxicity. The interaction of 9-methylguanine (9-MeG-N7) with complexes 1?3 was studied by 1H NMR and mass spectroscopy. Furthermore, DFT calculations have been performed on complexes 1?3 and also [M(bpy)(L)(9-MeG-N7)](NO3)(M = Pd(II), 4, Pt(II), 5) or [Au(bpy)(L)(9-MeG-N7)](NO3)2, 6, using the BP86-D and B3LYP* functionals to provide a complete rationalization of their structures and to describe their electronic structures. The energy decomposition analysis (EDA) gave a clear understanding of the bonding for all complexes 1?6 showing that the interactions are mostly governed by electrostatic ones. Strong interactions occurred between the chlorine anion and the metallic fragment, but weakened between 9-methylguanine and the metallic fragment, in agreement with the electron transfers and the interaction energies.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Based on the synthesis of curcumin and its derivatives from aromatic aldehydes, a novel series of palladium(II) complexes with curcumin (or its derivatives) and 2,2?-bipyridine have been synthesized through a directed self-assembly approach that involves spontaneous deprotonation of the curcuminoid ligands in H2O/acetone solution. These complexes have been characterized by 1H (13C) NMR, HRMS and elemental analysis. Crystal structure of 3h has been determined by X-ray diffraction analysis. Their cytotoxicity was tested by MTT. The preliminary results showed that complexes 3d, 3f, 3h have significant inhibition on proliferation of three carcinoma cells such as MCF-7, HeLa and A549 cells, which were more active than cisplatin. Further mechanistic studies indicated that the tested complex 3h arrested the cell cycle in the S phase and can disrupted mitochondrial membrane potential and induced tumor cell apoptosis through reactive oxygen species (ROS)-dependent pathway.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Palladium-catalysed cross-coupling reactions are some of the most frequently used synthetic tools for the construction of new carbon?carbon bonds in organic synthesis. In the work presented, Pd(II) complex catalysts were synthesized from palladium chloride and nitrogen donor ligands as the precursors. Infrared and 1H NMR spectroscopic analyses showed that the palladium complexes were formed in the bidentate mode to the palladium centre. The resultant Pd(II) complexes were tested as catalysts for the coupling of organobismuth(III) compounds with aryl and acid halides leading to excellent yields with high turnover frequency values. The catalysts were stable under the reaction conditions and no degradation was noticed even at 150C for one of the catalysts. The reaction proceeds via an aryl palladium complex formed by transmetallation reaction between catalyst and Ar3Bi. The whole synthetic transformation has high atom economy as all three aryl groups attached to bismuth are efficiently transferred to the electrophilic partner.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Abstract: Azacalixarenes have side arms (N-substituents) on the nitrogen atoms in their macrocyclic ring systems; thus, a variety of molecular designs are possible by modifying these side arms. This is a special feature of azacalixarene system which is not available in calix[n]arenes. In this paper, we used azacalix[3.1.3.1] and [3.1.1.1]arenes because these compounds have concave cavities. The cavity size of the azacalix[3.1.1.1] structure is small like the calix[4]arenes, but, supramolecular systems can be designed in which two or three azacalix units are connected by covalent or coordination bonds. Previously reported compounds, N-(4-picolyl)-[3.1.3.1] or [3.1.1.1]arenes, can be applied for this purpose. The 4-picolyl group can form covalent bonds with alkylation and form coordination bonds with a variety of transition metal ions. By using these bonds, we extend the cavity size of the azacalixarenes and construct newly designed supramolecular structures. We expected that these molecules would form larger molecular cavities upon side arm modification, and inclusion abilities of these cavities can be extended compared to the azacalixarenes of small cavity sizes. However, most of these molecular structures could not be determined, and none showed inclusion phenomena contrary to our expectations. Only the molecular structure of a p-xylylene-bridged molecule was confirmed, which possessed a self-inclusion structure in which the bridging unit (p-xylylene) was encapsulated by two azacalixarene cavities. Additionally, it was found that p-methyl-N-(4-picolyl)azacalix[3.1.1.1]arene 1 formed two molecular packing modes depending on the recrystallizing solvents. One is stacked structure by pi?pi interactions, and another is capsule type structure in which two solvent molecules were encapsulated. Graphic abstract: A self-inclusion type cage molecule was obtained by connecting N-(4-picolyl)azacalix[3.1.1.1]arene with a p-xylylene unit.[Figure not available: see fulltext.].

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method