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The Synthesis and Reactions of Palladium-Iron Carbonyl Complexes containing Bridging Ph2PCH2PPh2 Ligands

Treatment of tetrahydrofuran solution of FeI2 with two equivalents of Ph2PCH2PPh2 (dppm),under an atmosphere of CO, gave trans,mer- (1b) in high yield.The bromide analogue was prepared similarly but was unstable.Treatment of compound (1b) with (dba = dibenzylideneacetone) in benzene, under an atmosphere of CO, gave the bimetallic iron(I)-palladium(I) complex (2c).Complex (2c) was protonated by HBF4*OEt2 to give the cationic hydride BF4, wich was characterised only in solution.Treatment of (2c) with MeCN caused displacemeent of both iodide and carbonyl ligands from iron to give <(MeNC)3Fe(mu-dppm)2PdI>I, whereas treatment of (2c) with the bulky isocyanide ButNC displaced only iodide to give <(ButNC)(OC)2Fe(mu-dppm)2PdI>I.N.m.r. (1H- and 31P-<1H>)Nand i.r. data are reported.

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

New explortion of 32005-36-0

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Palladium-catalyzed oxidative carbonylation of 1-alkynes into 2-alkynoates with molecular oxygen as oxidant

A new preparative method to produce alkyl 2-alkynoates from 1-alkynes in alcohol under atmospheric pressure of CO at room temperature was developed with palladium-phosphine catalysts, using molecular oxygen as an oxidant. On the basis of the behavior of model complexes such as methoxycarbonylpalladium and alkynylpalladium complexes, we propose a mechanism accounting for the catalytic carbonylation of alkynes through an intermediate having the both methoxycarbonyl and alkynyl ligands that liberates methyl 2-alkynoates and a Pd(0) species on reductive elimination. The oxidation of Pd(0) to Pd(II) species in the presence of a halide ion was confirmed to proceed cleanly with molecular oxygen as the oxidant. On the basis of the findings on homogeneous catalysts, a heterogeneous catalytic system using Pd/C has also been developed.

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

New explortion of Bis(dibenzylideneacetone)palladium

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Linear and V-Shaped Alkynyl-1,3,5-triazines

A concise route for the synthesis of linear and V-shaped alkynyl-1,3,5-triazines has been developed by starting from 2,4-dichloro-1,3,5-triazine derivatives. The sequential substitution of the 2- and 4-chloro groups by a regioselective Sonogashira coupling reaction afforded symmetric and unsymmetric V-shaped alkynyl-1,3,5-triazines. A modulated copper-free Pd/1,10-phenanthroline catalyst system showed good compatibility with the -OCH3, -NPh2, and p-CH3OC6H4- substitutents and furnished the targeted linear alkynyl-1,3,5-triazines in good yields. A Pd/Ag bimetallic system afforded the desired symmetric and unsymmetric V-shaped alkynyl-1,3,5-triazines in moderate to good yields. The photophysical properties of the new alkynyl-1,3,5-triazine compounds were characterized experimentally. The X-ray diffraction analysis of 2a confirmed a coplanar position between the phenyl group and the 1,3,5-triazinal moiety. Intermolecular pi-pi interactions were observed between two of the TZ units, and the shortest atomic contact distance between the phenyl moieties of two adjacent molecules is 3.655 A. A protocol has been developed for the synthesis of alkynyl-1,3,5-triazines, especially unsymmetrical alkynyl-1,3,5-triazines with two different alkynyl groups on the triazine core. The Pd2(dba)3/1,10-phenanthroline catalyst system was used in a copper-free Sonogashira coupling reaction followed using a Pd/Ag bimetallic system for the subsequent alkynyl coupling step. dba = dibenzylideneacetone, 1,10-phen = 1,10-phenanthroline, DIPEA = N,N-diisopropylethylamine, and Tf = trifluoromethylsulfonyl.

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

Some scientific research about Tetrakis(acetonitrile)palladium(II) tetrafluoroborate

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Electrophilic metal precursors and a beta-diimine ligand for nickel(II)- and palladium(II)-catalyzed ethylene polymerization

The alpha-diimine ligand ArN=C(Me)C(Me)=NAr (Ar = 2,6-C6H3-iPr2) reacts with Pd(OAc)2 in the presence of HBF4·Et2O, or [Pd(MeCN)4](BF4)2 in the absence of acid, to give ethylene polymerization catalysts. The reactions of a related beta-diimine ligand with [Pd(MeCN)4]-(BF4)2 and (1,2-dimethoxyethane)NiBr2, and the polymerization activity of catalysts derived from it, are discussed.

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

Discovery of 32005-36-0

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Regioselectivity in the Sonogashira coupling of 4,6-dichloro-2-pyrone

The Sonogashira cross-coupling of 4,6-dichloro-2-pyrone with terminal acetylenes proceeds in good yields and high regioselectivity for the 6-position; dibenzylidene acetone (dba) type ligands play a non-innocent role in reactions mediated by Pd(dba)2/PPh3; theoretical studies indicate that C-6 oxidative addition is favoured both kinetically and thermodynamically.

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

Extracurricular laboratory:new discovery of 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex

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A divergent synthesis of oligoarylalkanethiols with Lewis-basic N-donor termini

Araliphatic thiols are key molecules for the formation of self-assembled monolayers with high long-range order. If these monolayers shall act as bases for the attachment of other molecules, the respective thiols need to carry suitable functional groups, such as the amino or the pyridine group. Due to their Lewis-basicity, these groups are not compatible with the thiol group under most reaction conditions. Here, an entry into this versatile class of compounds is presented, by using fundamental building blocks in which the thiol groups are protected as triisopropylsilyl sulfides making them compatible with many reagents including Grignard reagents and palladium catalysts. With this strategy at hand, six thiols with bi- and terphenyl backbones, one to three methylene groups, and amino or pyridine head groups became accessible in short reaction sequences. The Royal Society of Chemistry 2010.

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

More research is needed about Bis(tri-tert-butylphosphine)palladium

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Single-step synthesis of styryl phosphonic acids: Via palladium-catalyzed Heck coupling of vinyl phosphonic acid with aryl halides

We have developed a single step palladium-catalyzed Heck coupling of aryl halides with vinyl phosphonic acid to produce functionalized (E)-styryl phosphonic acids. This pathway utilizes a variety of commercially available aryl halides, vinyl phosphonic acid and Pd(P(tBu)3)2 as catalyst. These conditions produce a wide range of styryl phosphonic acids with high purities and good to excellent yields (31-80%).

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

More research is needed about Bis(dibenzylideneacetone)palladium

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Compound, containing bipyrazole ring, intermediate and application thereof (by machine translation)

The invention discloses a compound, containing double pyrazole rings . an intermediate thereof and an application I, and provides a compound with a double pyrazole ring as shown; and an application range of, of the compound as a ligand in, coupling and C – N coupling reaction C – C of aryl boronic acid and aryl chloride, in particular to a coupling, of aryl boronic acid and aryl chloride. (by machine translation)

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

Archives for Chemistry Experiments of Bis(dibenzylideneacetone)palladium

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Novel homo- and heterobimetallic palladium (0) and platinum(0) complexes of olefinic mono-, bis-, and tris-macrocyclic ligands

Molecular structures featuring two and three triolefinic 15-membered macrocycles of type 2 as well as their homo- and heterometallic complexes of palladium(0) and platinum(0) (5, 7) have been synthesized from 2,4,6-trichloro-1,3,5-triazine, 1. The strategy employed allows easy preparation of heterobimetallic complexes in a controlled manner. Several mass spectrometry techniques are useful to identify these complexes.

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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-catalyzed benzylation of arylboronic acids with N,N-ditosylbenzylamines

The palladium-catalyzed coupling of N,N-ditosylbenzylamines with arylboronic acids has been investigated, and the resulting diarylmethanes were obtained in high yields. Conversion of the amine to a N,N-ditosylimide group provided an efficient leaving group for the Pd-catalyzed benzylation of arylboronic acids.

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