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We report a general, high-yielding method for the synthesis of water-soluble complexes, which is based upon the weak-link approach to supramolecular coordination chemistry. Specifically, we have utilized oligomeric ethylene glycol functional groups appended to the aryl groups of the diphenylphosphine moieties to achieve solubility. Small molecules or halide ions can be used to expand these complexes into larger, more flexible macrocyclic structures. The realization of this approach should allow for the preparation of allosteric biomimetic structures which can be used in aqueous media.

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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 simple synthetic conversion of a 90-angled bis-pyridyl ligand into a tripodal tris-pyridyl ligand leads to the formal transformation of a cubic (a=b=c) into a square-cuboid (a=b?c) coordination cage. Mathematical considerations associated with the ligand design, together with X-ray structure results, NMR spectroscopic and mass spectrometric characterization and molecular modeling of both coordination cages are presented and discussed. Minecraft with molecules: The simple synthetic conversion of a 90-angled bis-pyridyl ligand into a tripodal tris-pyridyl ligand leads to the formal transformation of a cubic (a=b=c) into a square-cuboid (a=b?c) coordination cage. The ligand design based on mathematical considerations, X-ray structure results, NMR spectroscopic and mass spectrometric characterization and molecular modeling of both coordination cages are presented.

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

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Structurally flexible oligoisopyrazole molecules were self-assembled into discrete complexes with structural diversity upon palladium coordination. Structural convergence was controlled by a stoichiometry change to induce stepwise metal coordination of isopyrazole subunits. Three different types of complexes were selectively generated from a diisopyrazole ligand. Furthermore, tetraisopyrazole ligands were quantitatively assembled into a discrete complex in a predictable manner.

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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 heterogeneous catalysis, the catalyst is in a different phase from the reactants. category: catalyst-palladium, At least one of the reactants interacts with the solid surface in a physical process called adsorption in such a way. 21797-13-7, name is Tetrakis(acetonitrile)palladium(II) tetrafluoroborate. In an article,Which mentioned a new discovery about 21797-13-7

Reaction of the functionalised thioether crowns [14]aneS4-6-one (1,4,8,11-tetrathiacyclotetradecan-6-one, L1) and [10]aneS3-9-one (1,4,7-trithiacyclodecan-9-one, L2) with 2,4-dinitrophenylhydrazine in a protic solvent under acidic catalysis afforded the corresponding hydrazones L3 and L4, respectively, in high yield. Reaction of [14]aneS4-6-one with p-nitrophenylhydrazine under similar conditions affords the hydrazone L5. Reaction of L3 with [Pd(MeCN)4][BF4]2 in MeCN yielded the complex [Pd(L3)][BF4]2, while reaction of this ligand with [Pt(EtCN)4][CF3SO3]2 in MeCN afforded [Pt(L3)][CF3SO3]2. The single-crystal structures of L3-L5 and of [Pd(L3)][BF4]2 have been determined. In all cases, pi-pi stacking is observed, the free macrocycles crystallising as polymeric arrays of face-sharing hydrazone moieties. In [Pd(L3)]2+, pi-pi interactions alternate with face sharing between planar [PdS4]2+ units constructing a one-dimensional polymeric array. The hydrazone function forces distortions of the respective macrocyclic rings and imparts chirality to the [Pd(L3)]2+ cation. The potential of these molecules as building blocks for macrocyclic liquid crystals and extended supramolecular arrays is discussed, as is the need to consider steric factors in rationalising the reactivity of keto-functionalised thioether crowns.

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

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1,2,4,5-Tetrakis(phenyselenomethyl)benzene (L) has been synthesized by reaction of in situ generated PhSe- with 1,2,4,5- tetrakis(bromomethyl)benzene in N2 atmosphere. Its first bimetallic complexes and a bis-pincer complex having compositions [(eta3- C3H5)2Pd2(L)][ClO4] 2 (1) [Pd2(C5H5N) 2(L)][BF4]2 (2) and [(eta6-C 6H6)2Ru2(L)Cl2][PF 6]2 (3) have been synthesized by reacting L with [Pd(eta3-C3H5)Cl]2, [Pd(CH 3CN)4][BF4]2 and [(eta6-C6H6)2RuCl 2]2 respectively. The structures of ligand L and its all three complexes have been determined by X-ray crystallography. In 1 and 3, ligand L forms with two organometallic species seven membered chelate rings whereas in 2 it ligates in a bis-pincer coordination mode. The geometry around Pd in 1 or 2 is close to square planar whereas in 3, Ru has pseudo-octahedral half sandwich “Piano-Stool” geometry. The Pd-Se bond distances are in the ranges 2.4004(9)-2.4627(14) A and follow the order 1 > 2, whereas Ru-Se bond lengths are between 2.4945(16) and 2.5157(17) A. The 1 and 2 have been found efficient catalysts for Heck reaction of aryl halides with styrene and methyl acrylate. The 2 is superior to 1. The TON and TOF values (per Pd) are up to ? 47500 and ?2639 h-1 respectively. 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

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Control over the integrative self-sorting of metallo-supramolecular assemblies opens up possibilities for introducing increased complexity and function into a single self-assembled architecture. Herein, the relationship between the geometry of three ligand components and morphology of three self-sorted heteroleptic [Pd2L2L?2]4+ cages is examined. Pd-mediated assembly of two bis-monodentate pyridyl ligands with native bite angles of 75 and 120 affords a cis-[Pd2L2L?2]4+ cage while the same reaction with two ligands with bite angles of 75 and 60 gives an unprecedented, self-penetrating structural motif; a trans-[Pd2(anti-L)2L?2]4+ heteroleptic cage with a ?doubly bridged figure eight? topology. Each heteroleptic assembly can be formed by cage-to-cage conversion of the homoleptic precursors and morphological control of [Pd2L2L?2] cages is achieved by selective ligand displacement transformations in a system of three ligands and at least six possible cage 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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A series of [Pd2L4]4+(X-) 4 metallosupramolecular architectures have been synthesised where X- =, OTf-, OMs- or OTs- and L = 2,6-bis(pyridin-3-ylethynyl)pyridine. These systems have been characterised by NMR, IR and UV-vis spectroscopies, mass spectrometry, elemental analysis and, in several cases, by X-ray crystallography. Using these solution-and solid-state methods, we have investigated the exohedral and endohedral interactions of various anions with these cationic assemblies.

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

Awesome Chemistry Experiments For Tetrakis(acetonitrile)palladium(II) tetrafluoroborate

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The activation of O2 is a key step in selective catalytic aerobic oxidation reactions mediated by transition metals. The bridging trinuclear palladium species, [(LPdII)3(mu3- O)2]2+ (L=2,9-dimethylphenanthroline), was identified during the [LPd(OAc)]2(OTf)2-catalyzed aerobic oxidation of 1,2-propanediol. Independent synthesis, structural characterization, and catalytic studies of the trinuclear compound show that it is a product of oxygen activation by reduced palladium species and is a competent intermediate in the catalytic aerobic oxidation of alcohols. The formation and catalytic activity of the trinuclear Pd3O2 species illuminates a multinuclear pathway for aerobic oxidation reactions catalyzed by Pd complexes. Catalytic menage a trois: A catalytically active trinuclear Pd 3O2 complex was identified during Pd-mediated aerobic oxidation of alcohols. Synthesis, structural characterization, and catalytic studies of the trinuclear compound show that it is a product of oxygen activation by reduced palladium species and is a competent intermediate in the catalytic aerobic oxidation of alcohols. These results illuminate a new pathway for O2 reduction by Pd 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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Interlocked dimer 2, which is composed of two physically interlocked monomers 1, has three cavities (cavity A × 2 and cavity B × 1) and can encapsulate three anions, such as NO3 – and BF4 -, one anion per cavity. There are six possible encapsulation patterns, A-F; two (A and F) contain only one kind of anion and the others (B-E) contain both NO3 – and BF4 – at the same time with different ratios and with different positions. Anion competition experiments showed that in addition to F, which encapsulates three NO3 – ions, C, in which NO3 – and BF4 – ions are captured in cavities A and cavity B, respectively, was selectively formed. Detailed investigations have revealed that B-E were formed by dimerization, but three of the four were subjected to anion exchange and converged into C or F. This selective formation can be explained by the fact that NO3 – is a better anion template than BF4 -, as well as the molecular structure of the interlocked dimer; cavities A are surrounded by four bridging ligands and can be accessed by free anions, whereas no space available for anion exchange is present around cavity B because this cavity is surrounded by eight bridging ligands. Therefore, the BF4 – ions in cavities A are expelled by free NO3 -, but the BF4 – ion in cavity B is not, resulting in the selection of C and F. We have found that the volume of the cavity influenced anion recognition. New interlocked dimer 3, which has smaller cavities than those of 2, captured three NO3 – ions to form F, whereas only a small amount of an interlocked dimer that contains both NO3 – and BF4 – was formed.

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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 stability of five different [Pdn(N-donor)m]2n+ assemblies was examined by performing disassembly experiments with pyridine and with trifluoroacetic acid. Pyridine-induced disassembly was found to be most pronounced for Pd complexes containing N-donor ligands of low basicity. At the same time, these assemblies displayed high acid resistance. The contrasting stability in the presence of acid or pyridine can be used for the pH-controlled switching between different metallosupramolecular structures.

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