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The hydrogenolysis of mono- and dinuclear PdII hydroxides was investigated both experimentally and computationally. It was found that the dinuclear mu-hydroxide complexes {[(PCNR)Pd]2(mu-OH)}(OTf) (PCNH=1-[3-[(di-tert-butylphosphino)methyl]phenyl]-1H-pyrazole; PCNMe=1-[3-[(di-tert-butylphosphino)methyl]phenyl]-5-methyl-1H-pyrazole) react with H2 to form the analogous dinuclear hydride species {[(PCNR)Pd]2(mu-H)}(OTf). The dinuclear mu-hydride complexes were fully characterized, and are rare examples of structurally characterized unsupported singly bridged mu-H PdII dimers. The {[(PCNMe)Pd]2(mu-OH)}(OTf) hydrogenolysis mechanism was investigated through experiments and computations. The hydrogenolysis of the mononuclear complex (PCNH)Pd-OH resulted in a mixed ligand dinuclear species [(PCNH)Pd](mu-H)[(PCC)Pd] (PCC=a dianionic version of PCNH bound through phosphorus P, aryl C, and pyrazole C atoms) generated from initial ligand ?rollover? C?H activation. Further exposure to H2 yields the bisphosphine Pd0 complex Pd[(H)PCNH]2. When the ligand was protected at the pyrazole 5-position in the (PCNMe)Pd?OH complex, no hydride formed under the same conditions; the reaction proceeded directly to the bisphosphine Pd0 complex Pd[(H)PCNMe]2. Reaction mechanisms for the hydrogenolysis of the monomeric and dimeric hydroxides are proposed.

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

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There are provided novel compounds of formula (I) 1wherein R1, R2, R3, X and Z are as defined in the Specification and optical isomers, racemates and tautomers thereof and pharmaceutically acceptable salts thereof; together with processes for their preparation, compositions containing them and their use in therapy. The compounds are inhibitors of the enzyme nitric oxide synthase.

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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 new approach to the synthesis of benzothiophene-based palladium(II) complex of SCN unsymmetrical pincer-type ligand from iodocyclization of bis(methylthio)phenyl substituted ethynyl pyridine followed by oxidative addition of tris-(dibenzyledeneacetone) dipalladium(0) has been developed. The mechanistic implication of palladium complex reveals the practical evidence of oxidative addition step in Suzuki coupling reaction.

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

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Electric Literature of 52409-22-0, Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps.In a article, 52409-22-0, molcular formula is C51H42O3Pd2, introducing its new discovery.

Direct: With [Pd2(dba)3] as a catalyst, the direct alkynylation of thiophenes bearing a variety of substituents has been accomplished by using terminal alkynes as alkynylating reagents. This protocol is also applicable to other electron-rich aromatic heterocycles. dba=dibenzylidenacetone. Copyright

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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 catalytic method to synthesize 1,3,-dienes from propargylic precursors is reported. This palladium-catalyzed carbon-nitrogen bond-forming reaction furnishes 2-amino-1,3-dienes in excellent yields (up to 98%) and shows a broad tolerance to functional group diversity. The reaction has been demonstrated for over 30 amine substrates, including anilines and indoles, and proceeds under mild neutral conditions. The resulting 1,3-dienes are of great synthetic interest because of their further reaction potential.

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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 copper free [Pd]-catalyzed domino intramolecular Heck and intermolecular decarboxylative Sonogashira couplings, for the synthesis of alkyne bearing heterocyclic compounds with a quaternary carbon atom, is described. Notably, this dual bond forming strategy is successful in water solvent, under microwave irradiation. This one-pot operation enabled the formation of a variety of dihydrobenzofurans, indolines and oxindoles, in very good to near quantitative yields. Notably, unlike earlier reports, the present strategy is successful in delivering the products with short alkyl substituents on acetylene carbon, which is first of its kind.

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

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How molecular conformation variation due to the existence of steric torsions within the conjugated backbones plays a role in molecular packing and resultant polymer solar cell (PSC) performance was investigated by synthesizing two isomeric alternating D-A copolymers. In these copolymers, poly{3?,4?-dihexyl-(2,2?:5?,2??-terthiophene)-5,5??-diyl-alt-[4?,7?-di-2-(4-(2?-ethylhexyl))thienyl-(5?,6?-difluorobenzo[c][1?,2?,5?]thiadiazole)]-5,5-diyl} (PTDTffBT(C6/EH)) and poly{3?,4?-di(2?-ethylhexyl)-(2,2?:5?,2??-terthiophene)-5,5??-diyl-alt-[4?,7?-di-2-(4-hexyl) thienyl-(5?,6?-difluorobenzo[c][1?,2?,5?]thiadiazole)]-5,5-diyl} (PTDTffBT(EH/C6)), which had comparable molecular weight, the linear hexyl and branched 2-ethylhexyl chains are interchanged between the donor and the acceptor units. Such molecular design could offer two isomeric donors with limited conformational steric distortions by positioning the given alkyl chains with fine steric disparity in the same conjugated backbone. The interchange of the side chains caused a fluctuation of ?5 of the dihedral angles between the thiophenes within the donor units and between the ending thiophenes from the adjacent donor and acceptor units. The subtle transform on backbone steric distortions of the two copolymers leads to a negligible impact on electronic structures but a distinct one on molecular packing in film. The copolymers both embody polymorph molecular packing with preferential edge-on orientation in neat films. The (100) and (010) distance, corresponding to the lamellar stacking between the alkyl chains and the pi-pi stacking between the conjugated backbones, are both improved in the PTDTffBT(C6/EH) film with enhanced crystallinity than that in the PEDTffBT(EH/C6) film. Similar molecular packing feature remains for the BHJ blends of the two copolymers with the acceptor of PC71BM. Moreover, PTDTffBT(C6/EH) exhibits the apparant coexistence of face-on orientation with improved crystallinity. The PTDTffBT(C6/EH): PC71BM PSC devices offer a much improved maximum power conversion efficiency (PCE) of 8.24% over 6.13% of the PTDTffBT(EH/C6) device, mainly due to more efficient charge generation and balanced charge transport resulted from the optimized film microstructure. The investigation clearly shows the sensitivity of molecular packing and corresponding PSC device performance to subtle steric distortions within conjugated backbones.

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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 signalling molecularly imprinted polymer was synthesised for easy detection of tamoxifen and its metabolites. 6-Vinylcoumarin-4-carboxylic acid (VCC) was synthesised from 4-bromophenol to give a fluorescent monomer, designed to switch off upon binding of tamoxifen. Clomiphene, a chlorinated analogue, was used as the template for the imprinting, and its ability to quench the coumarin fluorescence when used in a 1:1 ratio was demonstrated. Tamoxifen and 4-hydroxytamoxifen were also shown to quench coumarin fluorescence. Imprinted and non-imprinted polymers were synthesised using VCC, methacrylic acid as a backbone monomer and ethylene glycol dimethacrylate as cross-linker, and were ground and sieved to particle sizes ranging between 45 and 25 mum. Rebinding experiments demonstrate that the imprinted polymer shows very strong affinity for both clomiphene and tamoxifen, while the non-imprinted polymer shows negligible rebinding. The fluorescence of the imprinted polymer is quenched by clomiphene, tamoxifen and 4-hydroxytamoxifen. The switch off in fluorescence of the imprinted polymer under these conditions could also be detected under a UV lamp with the naked eye, making this matrix suitable for applications when coupled with a sample preparation 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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The present invention provides transition-metal-catalyst-based methods for the arylation and vinylation of activated methyl, methylene, and methine carbons with aryl halides, vinyl halides, and the like. The methods of the invention provide several improvements over existing methods, including the ability to synthesize efficiently and under mild conditions alpha-aryl and alpha-vinyl products from a wide range of starting materials, including ketones, esters, hydrazones, and imines. Furthermore, the methods of the invention may be used in an asymmetric sense, i.e. to produce enantiomerically-enriched chiral alpha-aryl and alpha-vinyl products.

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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 Pd-benzothiazol-2-ylidene complex I was found to be a chemoselective catalyst for the Tsuji-Trost allylation of active methylene compounds carried out under neutral conditions and using carbonates as allylating agents. The proposed protocol consists in a simplified procedure adopting an in situ prepared catalyst from Pd2dba3 and 3-methylbenzothiazolium salt V as precursors. A comparison of the performance of benzothiazole carbene with phosphanes and an analogous imidazolium carbene ligand is also proposed.

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