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Factors determining the chemoselectivity of phosphorus-modified palladium catalysts in the hydrogenation of chloronitrobenzenes

The precursor nature effect on the state of the Pd?P surface layer in palladium catalysts and on their properties in the liquid-phase hydrogenation of chloronitrobenzenes under mild conditions has been investigated. A general feature of the Pd?P-containing nanoparticles obtained from different precursors and white phosphorus at P/Pd = 0.3 (PdCl2 precursor) and 0.7 (Pd(acac)2 precursor) is that their surface contains palladium in phosphide form (BE(Pd3d5/2) = 336.2 eV and BE(?2?) = 128.9 eV) and Pd(0) clusters (BE(Pd3d5/2) = 335.7 eV). Factors having an effect on the chemoselectivity of the palladium catalysts in chloronitrobenzenes hydrogenation are considered, including the formation of small palladium clusters responsible for hydrogenation under mild conditions.

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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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Chemical synthesis and biological evaluation of palmerolide A analogues

Molecular design and chemical synthesis of several palmerolide A analogues allowed the first structure activity relationships (SARs) of this newly discovered marine antitumor agent. From several analogues synthesized and tested (ent-1, 5-14, 21-26, 50, 51), compounds 25 (with a phenyl substituent on the side chain) and 51 (lacking the C-7 hydroxyl group) were the most interesting, exhibiting approximately a 10-fold increase in potency and equipotency, respectively, to the natural product. These findings point the way to more focused structure activity relationship studies.

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

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Flexible coordination of diphosphine ligands leading to cis and trans Pd(0), Pd(II), and Rh(I) complexes

A series of diphosphine ligands iPr2P-C 6H4-X-C6H4-PiPr 2 (for ligand L1, X = CH2; for ligand L 2, X = CH2CH2) was investigated to determine the preference for cis/trans coordination to palladium(0), palladium(II), and rhodium(I). Increasing the length of the bridging alkyl backbone from one to two carbons changes the geometry of the resulting palladium(II) complexes, with L1 coordinating preferentially cis, while L2 coordinates in a trans fashion. Coordination to Pd(0) leads to L1Pd(dba) and L2Pd(dba), in which both ligands accommodate a P-M-P angle close to 120. L2 was found to coordinate cis in a rhodium(I) complex ([L2Rh(nbd)][BF4], where nbd = norbornadiene).

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

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Palladium-TCNQ-based charge-transfer complexes (TCNQ = 7,7?-8,8-tetracyanoquinodimethane)

The reaction between the palladium(0) complex [Pd(dba)2] (dba = dibenzylidenacetone) with TCNQ proceeds via an electron-transfer process leading to a solid having the empirical formula [Pd(TCNQ)2(CH3CN)x] (x < 1). The same reaction performed in the presence of a variety of ligands leads to compounds whose nature is dependent on the geometrical and electronic properties of the ligands. [Pd(dba)2] reacts with TCNQ in the presence of 2,2?-bipyridine (bipy) affording, depending on the experimental conditions, two charge-transfer (CT) solids of general formula [Pd( bipy)2(TCNQ)2], one of which exhibits spectral features of conducting TCNQ complexes. When the reaction is performed in the presence of the more steric demanding bis-chelating ligand, 2,9-dimethylphenanthroline (dmphen), the palladium complex [Pd(dmphen)(pi-TCNQ)] is obtained. A complex with a similar stoichiometry and spectroscopic properties is obtained by reacting [Pd(dba)2] with TCNQ in the presence of PPh3, while by using the bis-chelating 1,2-bis(diphenylphosphino)ethane (dppe) ligand the CT salt [Pd(dppe)2] [TCQM]2 is obtained. The CT complex [Pd(terpy)(eta1-TCNQ)] [TCNQ] is the product of the reaction of [Pd(dba)2] and TCNQ in the presence of the ter-chelating 2,2?:6?,2?-terpyridine ligand (terpy). All compounds have been characterized by UV-Vis/ near-IR and IR spectroscopic techniques, X-ray photoelectron (XP) and Auger electron (XAE) spectroscopy have been employed to determine the formal charge on the palladium metal. If you are interested in 32005-36-0, you can contact me at any time and look forward to more communication. Recommanded Product: Bis(dibenzylideneacetone)palladium

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

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Aryl-phenyl scrambling in intermediate organopalladium complexes: A gas-phase study of the mizoroki-heck reaction

The intramolecular aryl-phenyl scrambling reaction within palladium-DPPP-aryl complex (DPPP=1,3-bis(diphenylphosphino)propane) ions was analyzed by state-of-the-art tandem MS, including gas-phase ion/molecule reactions. The Mizoroki-Heck cross-coupling reaction was performed in the gas phase, and the intrinsic reactivity of important intermediates could be examined. Moreover, linear free-energy correlations were applied, and a mechanism for the scrambling reaction proceeding via phosphonium cations was assumed.

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

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The coupling reactions of aryl halides and phenols catalyzed by palladium and MOP-type ligands

Palladium-catalyzed coupling reactions of aryl halides and phenols are described employing the bulky and electron-rich MOP-type ligands. When K3PO4 was used as base and toluene as solvent, the catalyst system exhibited high efficiency for the coupling reaction of the activated aryl halides. When NaH was used as base and o-xylene as solvent, unactivated aryl halides can be used as substrates.

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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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Heterometallic complexes with cube-type [MTi3N4] cores containing Group 10 metals in a variety of oxidation states

Treatment of [{Ti(eta5-C5Me5)(mu-NH)}3(mu3-N)] (1) with one equivalent of [Ni(cod)2] (cod = 1,5-cyclooctadiene) in toluene at 60-80C and subsequent addition of diphenylacetylene, trans-stilbene or triphenylphosphane afforded the nickel(0) complexes [LNi{(mu3-NH)3Ti3(eta5-C5Me5)3(mu3-N)}] (L = PhCCPh (2), PhCHCHPh (3), PPh3 (4)). The nickel(ii) complex [I2Ni{(mu3-NH)3Ti3(eta5-C5Me5)3(mu3-N)}] (5) was prepared by analogous addition of iodine to the solution obtained from the heating of 1 and [Ni(cod)2]. Treatment of 1 with one equivalent of [Pd(dba)2] (dba = dibenzylideneacetone) in toluene at room temperature led to the palladium(0) complex [(dba)Pd{(mu3-NH)3Ti3(eta5-C5Me5)3(mu3-N)}] (6). Compound 6 reacted immediately with chloroform-d1 to give the palladium dichloride derivative [Cl2Pd{(mu3-NH)2Ti3(eta5-C5Me5)3(mu-NH)(mu3-N)}] (7), which was prepared by treatment of 1 with [PdCl2(cod)] at room temperature. Addition of iodine to a toluene solution of 6 afforded the analogous palladium(ii) derivative [I2Pd{(mu3-NH)2Ti3(eta5-C5Me5)3(mu-NH)(mu3-N)}] (8). Complex 6 reacted with two equivalents of dimethylacetylenedicarboxylate (dmad) to give the metallacyclopentadiene palladium(ii) complex [{(MeOOC)4C4}Pd{(mu3-NH)2Ti3(eta5-C5Me5)3(mu-NH)(mu3-N)}] (9) via oxidative coupling. The treatment of 1 with [Pt(nbe)3] (nbe = norbornene) in toluene at room temperature gave the platinum(0) complex [(nbe)Pt{(mu3-NH)3Ti3(eta5-C5Me5)3(mu3-N)}] (10). Compound 10 reacted with excess iodine to afford the platinum(iv) ionic derivative [I3Pt{(mu3-NH)3Ti3(eta5-C5Me5)3(mu3-N)}]2(I3)(I5) (11) via an intermediate platinum(ii) complex [I2Pt{(mu3-NH)2Ti3(eta5-C5Me5)3(mu-NH)(mu3-N)}] (12). The X-ray crystal structures of 5, 8, 9 and 11 have been determined.

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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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Palladium(0)-dibenzylidene acetone complexes

Palladium(0)-dibenzylidene acetone complexes Pdx(dba)y, with y/x being from 1.5 to 3, are provided according to the invention at a purity of at least 99.5 wt. %. The use of said Pdx(dba)y complexes according to the invention is for determining their stoichiometry by means of elemental analysis. In the method for the production of Pdx(dba)y complexes from a Pd-containing educt and dibenzylidene acetone (dba) in alcohol, according to the invention a solution of the dba in alcohol pre-heated to more than 40 C. is provided first and then the Pd-containing educt is added to the pre-heated solution upon which the complexes are precipitated by a base.

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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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Asymmetric allylic C-H oxidation for the synthesis of chromans

An enantioselective intramolecular allylic C-H oxidation to generate optically active chromans has been accomplished under the cooperative catalysis of a palladium complex of chiral phosphoramidite ligand and 2-fluorobenzoic acid. Mechanistic studies suggest that this reaction commences with a Pd-catalyzed allylic C-H activation event and then undergoes asymmetric allylic alkoxylation. The synthetic significance of the method has been embodied by concisely building up a key chiral intermediate to access (+)-diversonol.

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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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Palladium(0) complexes with unsymmetric bidentate nitrogen ligands for the stereoselective hydrogenation of 1-phenyl-1-propyne to (Z)-1-phenyl-1-propene

A series of zerovalent palladium complexes Pd(NN(alkene) of bi- or tridentate nitrogen ligands of the general formula 6-R?-C5H3N-(C(R?)=NR)-2 (R? = H, Me, CH=NR?; R? = H, Me; R = alkyl, aryl, or amino group) and dimethylfumarate (dmfu) have been prepared and were subsequently employed as precatalysts in the homogeneous stereoselective semihydrogenation of 1-phenyl-1-propyne. An X-ray structure of Pd(C5H4N-(C(Me)=Ni-Pr)-2)(dmfu) was obtained. Whereas only relative small changes in substituents apply, the various complexes show very different stabilities under hydrogenation conditions. The complex Pd-(C5H4N-(C(H)=N(CH2)2OH)-2)(dmfu) exhibits a good selectivity for the (Z)-alkene but decomposes just before full conversion of the alkyne, whereas the complex Pd(C5H4N-(C(H)= Nz-Pr)-2)(dmfu) exhibits a good selectivity and stability under hydrogenation conditions and is a suitable catalyst for the stereoselective hydrogenation of 1-phenyl-l-propyne to (Z)-l-phenyl-1-propene.

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