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Pd K-edge X-ray absorption near-edge spectroscopy (XANES) is used to probe the unoccupied molecular orbitals in bidentate diphosphine Pd complexes. Complexes containing a series of bidentate diphosphine ligands (PP) are examined to study the effect of the ligand bite angle on the charge redistribution in these complexes. Different coordinating moieties (XX) have been used to induce a range of Pd oxidation states. A full interpretation of the Pd K-edge XANES data is presented. The negative second derivative of these XANES data provides direct information on the energy and electronic distribution of the different unoccupied molecular orbitals probed. The charge redistributions within the complexes, as reflected in the effective Pd oxidation state, are indicated by both the intensity of the first edge feature, the “Pd d peak”, and the energy of the second edge feature, the “Pd p peak”, which can be easily observed in the negative second derivative of the XANES data. Additionally, the changing covalent interaction between the Pd and coordinated moieties via the Pd p orbitals is reflected directly in the energy splitting of the “Pd p” peak. Thus, investigation of these (PP)Pd(XX) complexes, some used as catalysts in organic synthesis, with XANES spectroscopy provides new essential information on their electronic properties. Further, the XANES analysis techniques described in this paper can be applied to investigate the unoccupied molecular orbitals and charge redistributions within a wide range of samples.

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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 synthesis of new alkynyl-derived 2,5-disubstituted 1,3,4-oxadiazoles through palladium/copper-catalyzed Sonogashira cross-coupling between oxadiazole-substituted phenyl bromides and various arylacetylenes is described. Investigation of the absorption and emission spectra of the target compounds indicates emission profiles in the near-blue and blue region and high luminescence intensities. The presented approach is very convenient for the synthesis of luminescent small-molecules or precursors of other complex derivatives that are useful in the preparation of OLEDs as electron-transporting components.

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

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In homogeneous catalysis, the catalyst is in the same phase as the reactant. The number of collisions between reactants and catalyst is at a maximum.In a patent, 95464-05-4, name is 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex, introducing its new discovery. Recommanded Product: 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex

The total synthesis of the originally assigned structure of vannusal B (2) and its diastereomer (d-2) are described. Initial forays into these structures with model systems revealed the viability of a metathesis-based approach and a SmI2-mediated strategy for the key cyclization to forge the central region of the molecule, ring C. The former approach was abandoned in favor of the latter when more functionalized substrates failed to enter the cyclization process. The successful, devised convergent strategy based on the SmI 2-mediated ring closure utilized vinyl iodide (-)-26 and aldehyde fragment (±)-86 as key building blocks, whose lithium-mediated coupling led to isomeric coupling products (+)-87 and (-)-88 (as shown in Scheme 17 in the article). Intermediate (-)-88 was converted, via (-)-89 and (-)-90/(+)-91, to vannusal B structure 2 (as shown in Scheme 18 in the article), whose spectroscopic data did not match those reported for the natural product. Similarly, intermediate (+)-25, obtained through coupling of vinyl iodide (-)-26 and aldehyde (±)-27 (as shown in Scheme 13 in the article) was transformed via intermediates (-)-97 and (+)-98 (as shown in Scheme 19 in the article) to diastereomeric vannusal B structure (+)-d-2 (as shown in Scheme 19 in the article) which was also proven spectroscopically to be non-identical to the naturally occurring substance. These investigations led to the discovery and development of a number of new synthetic technologies that set the stage for the solution of the vannusal structural conundrum.

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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 present invention involves a process for preparing substituted indoles, such as DTSI involving two sequential cross-coupling reactions.

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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 present invention relates to chemical compounds having a general formula I wherein A1-8, D?, L1, L2, R1, R6-8 and n are defined herein, and synthetic intermediates, which are capable of modulating various protein kinase receptor enzymes and, thereby, influencing various disease states and conditions related to the activities of such kinases. For example, the compounds are capable of modulating Aurora kinase thereby influencing the process of cell cycle and cell proliferation to treat cancer and cancer-related diseases. The invention also includes pharmaceutical compositions, including the compounds, and methods of treating disease states related to the activity of Aurora kinase.

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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 transition metal catalysed reactions of benzaldehydes and benzylideneamines with disilanes have been investigated. Palladium phosphine complexes catalyse the double silylation of the C=O bond in benzaldehydes and the C=N bond in benzylideneamines with 1,2-difluoro-1,1,2,2-tetramethyldisilane to yield alpha-(fluorodimethylsilyl)-alpha-(fluorodimethylsiloxy)toluene and N-methyl-N-(fluorodimethylsilyl)-alpha-(fluorodimethylsilyl)benzylamine respectively. When less activated disilanes such as 1,2-dichloro- and 1,2-dimethoxy-1,1,2,2-tetramethyldisilane were employed, the palladium phosphine complexes were less active and selective, resulting in extensive side reactions inclusive of 1,2-disiloxy-1,2-diphenylethane formation. The reaction of benzophenone with the difluorodisilane formed 2,2-dimethyl-4,4,5,5-tetraphenyl- 1,3-dioxa-2-silacyclopentane without affording the corresponding simple double silylation product. The formation of side products such as 1,2-disiloxy-1,2- diphenylethane in the reaction of benzaldehyde and 2,2-dimethyl-4,4,5,5- tetraphenyl-1,3-dioxa-2-silacyclopentane in the reaction of benzophenone appears to suggest intermediacy of radical and silylene species. Tris(dibenzylideneacetone)diplatinum-etpo (etpo = 4-ethyl-1-phospha-2,6,7- trioxabicyclo[2.2.2]octane catalyst system was more active for unactivated disilanes, catalysing double silylation of benzaldehydes with hexamethyldisilane. The same catalyst system was found to catalyse the ortho silylation of benzylideneamines with disilanes via intramolecular C-H activation; both mono- and bis-silylated products were obtained. Reaction rates and product distributions are rationalised in terms of the steric and electronic properties of the disilanes, substrates and the catalyst used. The Royal Society of Chemistry 2003.

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

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Dichloro<1,1'-bis(diphenylphosphino)ferrocene>palladium(II) was found to catalyze the reaction of allylic alcohols with 2-octylmagnesium chloride and 1-phenylethylmagnesium chloride to give the corresponding cross-coupling products in high yields.

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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 series of homochalcogenide and mixed-chalcogenide ligand complexes of palladium and platinum have been prepared from the reactions of Pd(dppf)Cl2, (dppf = 1,1?-bis(diphenylphosphino)ferrocene), Pd(dippf)Cl2 (1,1?-bis(diisopropylphosphino)ferrocene), and Pt(dppf)Cl2 with 1,2-benzenedithiol (HSC6H4SH) (a), 3,4-toluenedithiol (HSC6H3MeSH) (b), 3,6-dichloro-1,2-benzenedithiol (HSC6H2Cl2SH) (c), 2-mercaptophenol (HSC6H4OH) (d), thiosalicylic acid (HSC6H4CO2H) (e) and thionicotinic acid (HSC6H3NCO2H) (f). Single-crystal X-ray diffraction studies show that all complexes have distorted square-planar geometry. The complexes undergo two quasi-reversible or irreversible one-electron redox processes that involve the chalcogen ligands and diphosphinoferrocene ligands. The oxidation potentials of the chalcogen ligands increase when they bear electron-withdrawing substituents.

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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 invention discloses a palladium catalyzed 1, 2 – trans-diaryl olefin preparation method, comprises the following steps: in the catalyst, cocatalyst and under the action of alkali, aryl acrylic acid and paratoluene sulfonic acid aromatic ester in the organic solvent in the reaction escapes suosuo the coupling, after the reaction is finished after treatment to obtain the 1, 2 – trans-diaryl olefin. The method through the C – O on the fracture of the key, the operation is simple, the use of relatively cheap and stable palladium catalyst, substrate good applicability, without harsh reaction conditions and strong alkali is added, can highly selectively generating trans 1, 2 – diaryl olefin. (by machine translation)

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

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High selectivity and yield from aryl-aryl coupling reactions between chlorine-containing aromatic bromides and organoboron reagents are reported. The variable reaction selectivity between the bromine and chlorine mainly depends on the electronic effects of the aromatic substrates. The reactivity of the chlorine can be completely restrained by employing the optimized Palladium catalysts, which can be used for the preparation of the chlorine-bearing molecules. Then, a series of high molecular weight conjugated copolymers with chlorine on the backbones are straight forward synthesized for the first time under Suzuki condensation reaction. The polymers show large Stokes shifts and low self-absorption. Efficient and high brightness red emission centre at about 636 nm can be obtained when doping the resulting polymer into F8BT.

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