Discovery of (2,2¡ä-Bipyridine)dichloropalladium(II)

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Pd complexes with trans-chelating ligands composed of two pyridyl groups and rigid pi-conjugated backbone

1,2-Bis(2-pyridylethynyl)benzene derivatives, having two pyridyl groups and pi-conjugated backbone, were prepared from the 1:2 Sonogashira reaction of 1,2-diiodobenzene with 2-alkynyl pyridines. The obtained ligands react with the palladium(II) complexes such as [PdCl2(cod)] and [PdCl 2(MeCN)2] to form the complexes with the ligands coordinated in a trans-chelating bidentate mode. The ligand obtained from 1,3-diiodobenzene and 2-alkynyl pyridine bridges two Pd(II) centers, yielding a dipalladium complex. A dichloropalladium complex with the trans-chelating ligand, containing two methoxy groups in the central arylene group, promotes coupling of phenyl lithium and of phenyl acetylene to yield the respective homo-coupling products. The ligand displacement reactions of {bis(2-pyridylethynyl)benzene}palladium(II) complex with phosphine and dinitrogen ligands, such as PPh3, dppe, dppb, en, tmeda, bpy and phen, takes place smoothly to release the trans-chelating ligand.

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

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Vinylidenation of Organoboronic Esters Enabled by a Pd-Catalyzed Metallate Shift

Organoboron ?ate? complexes undergo a net vinyl insertion reaction to give 1,1-disubstituted alkenyl boronic esters when treated with stoichiometric allyl acetate and a palladium catalyst. Reactions that employ vinyllithium afforded good to excellent yields after one hour, while reactions that employ vinylmagnesium chloride furnished modest to good yields after 18 hours.

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

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Highly selective Palladium-catalyzed Suzuki coupling reaction toward chlorine-containing electroluminescence polymers

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

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Bis-ZnII salphen complexes bearing pyridyl functionalized ligands for efficient organic light-emitting diodes (OLEDs)

Inspired by the emissive features of ZnII complexes based on bis-Schiff base ligands, bis-ZnII salphen complexes bearing pyridyl functionalized ligands have been successfully synthesized. Their photophysical features, electrochemical behavior and electroluminescent (EL) properties have been investigated in detail. The functionalized bis-ZnII salphen complexes can exhibit high thermal stability up to 417 C, and their photoluminescence (PL) spectra show a maximal emission wavelength peak at ca. 565 nm both in solution and PMMA doped films. The PL investigation of the neat films for these functionalized bis-ZnII salphen complexes indicated that the pyridyl functionalized ligands can effectively reduce the degree of molecular aggregation to enhance their emission intensity. Taking advantage of the charge carrier injection/transporting ability of the pyridyl functionalized ligands and their dendritic design, the optimized EL devices fabricated by a simple solution-processing method can achieve a peak luminance (Lmax) of 3589 cd m-2, a maximal external quantum efficiency (etaext) of 1.46%, a maximal current efficiency (etaL) of 4.1 cd A-1 and a maximal power efficiency (etap) of 3.8 lm W-1. These results should afford important instructions for exploiting high performance fluorescent emitters based on dinuclear ZnII complexes.

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

Awesome and Easy Science Experiments about 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex

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Modular synthesis of asymmetric rylene derivatives

The modular synthesis of asymmetric rylenes from naphthalic anhydride derivatives is presented. Imidization, Suzuki-Miyaura coupling and cyclodehydrogenation reactions are utilized for the generation of novel functional rylenes with these three core transformations providing significant flexibility over the final structure. The combination of simple purification and high yields enables access to asymmetric rylenes with functional handles at the imide-position and site-specific incorporation of bay position substituents. The resulting library of perylenes and bisnapthalimide-anthracene derivatives showcase the presented methodology and the ability to tune optoelectronic and electrochemical properties.

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

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Regiocontrolled palladium-catalyzed arylative cyclizations of alkynols

Tuning the reactivity of arylpalladium intermediates enables control of catalytic arylative 5-exo and 6-endo cyclizations of alkynols. The two modes of cyclizations represent a rare example of controllable, regioselective difunctionalization of alkynes. The cyclizations are useful in offering a divergent synthesis of oxygen-containing heterocycles, which is of synthetic use for further derivatization. Formal synthesis of an hNK-1 receptor antagonist also showcases the utility of our arylative cyclization.

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

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2,2?-Bipyridine-1,2-dithiolate mixed ligand complexes. Synthesis, characterisation and EPR spectroscopy

A series of new 2,2?-bipyridine/1,2-dithiolate transition metal complexes has been synthesised and characterised. As 1,2-dithiolate ligands 1,2-dithiooxalate (dto) and 1,2-dithiosquarate (dtsq) were used. It follows from the IR spectra that the multidentate dithiolate ligands coordinate exclusively via their sulfur atoms forming anMN2S2 coordination sphere. The central metal ions (M) are Cu2+, Ni2+, Pd 2+, Pt2+, and Zn2+. The complex Cu II(bpy)(dto)) could be studied by EPR spectroscopy and was measured as powder, diamagnetically diluted in the isostructural NiII(bpy) (dto)) host structure. The spin density contribution calculated from the experimental parameters is compared with the electronic situation in the frontier orbitals, namely in the semi-occupied SOMO of the copper complex, derived from quantum chemical calculations on different levels (EHT and DFT).

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

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Mixed neutral compounds of palladium(II) and platinum (II) chelated by diolato(2-) and di-imine ligands

The synthesis and characterization are described for compounds abbreviated (a) 1-5: [Pd(phen)(OO)], where OO = the dianion from 1,2-ethanediol (1), (+)-1,2-propanediol (2), (¡À)-2,3-butanediol (3), (-)-1,2-butanediol (4), catechol (5); (b) the sulphur analogue (6) [Pd(phen)(SCH2CH2S)], from ethane-1,2-dithiol; (c) the platinum analogue (7) [Pt(phen)(OCH2CH2O)]; (d) the 2,2?-bipyridyl analogue (8), [Pd(bipy)(OCH2CH2O)] (phen = 1,10-phenanthroline and bipy = 2,2?-bipyridyl).

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

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Substituted Imidazopyridines as HDM2 Inhibitors

The present invention provides substituted imidazopyridines as described herein or a pharmaceutically acceptable salt or solvate thereof. The representative compounds are useful as inhibitors of the HDM2 protein. Also disclosed are pharmaceutical compositions comprising the above compounds and potential methods of treating cancer using the same.

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

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Synthesis of 5-Arylpyrrole-2-carboxylic Acids as Key Intermediates for NBD Series HIV-1 Entry Inhibitors

5-Arylpyrrole-2-carboxylic acids are important key intermediates in the synthesis of HIV-1 entry inhibitors (such as NBD-11021 and NBD-14010). Here we present a general method for the synthesis of some 5-arylpyrrole-2-carboxylic acids in three steps starting from pyrrole. By this method, the compounds could be prepared on gram scale and without chromatographic purification.

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