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Dynamic formation of self-organized corner-connected square metallocycles by stoichiometric control

Corner-connected molecular squares were self-assembled from a three-component system formed by a bidentate ligand and two palladium or platinum complexes. The system is dynamic and the constitution of the species in solution can be modulated under stoichiometric control.

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

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Bis(acetonitrile-N)(1,4,8,12-tetraazacyclopentadecane)nickel(II) bis(triiodide) and (1,4,8,12-tetraazacyclopentadecane)-palladium(II) bis(triiodide)

In the first title compound, [Ni(C2H3N)2(C11H26N 4)]-(I3)2, the NiII centre is coordinated octahedrally: all four N-donor atoms of the macrocyclic ligand occupy an equatorial plane and the coordination is completed by two axial acetonitrile ligands. Each N – H group forms a contact of 2.97-3.11 A to one I atom of an I3- anion. One of these anions participates in long I…I contacts of 4.008 (3) A to form infinite chains of symmetry-related anions. In the second title compound, [Pd(C11H26N4)](I3)2, each PdII centre is coordinated in an equatorial plane by four N-donor atoms from the macrocyclic ligand and axially by a terminal iodine from each of two I3- anions at 3.525 (4) A. The same I atom forms an I…I contact of 4.094 (3) A such that cations and pairs of anions alternate within one-dimensional zigzag chains.

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

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Metal and Organic Templates Together Control the Size of Covalent Macrocycles and Cages

Covalent macrocycles and three-dimensional cages were prepared by the self-assembly of di- or tritopic anilines and 2,6-diformylpyridine subcomponents around palladium(II) templates. The resulting 2,6-bis(imino)pyridyl-PdII motif contains a tridentate ligand, leaving a free coordination site on the PdII centers, which points inward. The binding of ligands to the free coordination sites in these assemblies was found to alter the product stability, and multitopic ligands could be used to control product size. Multitopic ligands also bridged metallomacrocycles to form higher-order supramolecular assemblies, which were characterized via NMR spectroscopy, mass spectrometry, and X-ray crystallography. An efficient method was developed to reduce the imine bonds to secondary amines, leading to fully organic covalent macrocycles and cages that were inaccessible through other means.

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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

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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

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Pd(II) complexes containing N-alkyl-3-pyridine-5-trifluoromethyl pyrazole ligands: Synthesis, NMR studies and X-ray crystal structures

Palladium [PdCl2(L)] complexes with N-alkylpyridylpyrazole derived ligands [2-(5-trifluoromethyl-1H-pyrazol-3-yl)pyridine (L1), 2-(1-ethyl-5-trifluoromethyl-1H-pyrazol-3-yl)pyridine (L2), 2-(1-octyl-5-trifluoromethyl-1H-pyrazol-3-yl)pyridine (L3), and 2-(3-pyridin-2-yl-5-trifluoromethyl-pyrazol-1-yl)ethanol (L4) were synthesised. The crystal and molecular structures of [PdCl2(L)] (L = L2, L3, L4) were resolved by X-ray diffraction, and consist of monomeric cis-[PdCl2(L)] molecules. The palladium centre has a typical square-planar geometry, with a slight tetrahedral distortion. The tetra-coordinate metal atom is bonded to one pyridinic nitrogen, one pyrazolic nitrogen and two chlorine ligands in cis disposition. Reaction of L (L2, L4) with [Pd(CH3CN)4](BF4)2, in the ratio 1M:2L, gave complexes [Pd(L)]2(BF4)2. Treatment of [PdCl2(L)] (L = L2, L4) with NaBF4 and pyridine (py) and treatment of the same complexes with AgBF4 and triphenylphosphine (PPh3) yielded [Pd(L)(py)2](BF4)2 and [Pd(L)(PPh3)2](BF4)2 complexes, respectively. Finally, reaction of [PdCl2(L4)] with 1 equiv of AgBF4 yields [PdCl(L4)](BF4).

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

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Construction of Natural-Product-Like Cyclophane-Braced Peptide Macrocycles via sp3 C-H Arylation

Cyclic peptides have provided one of the most important platforms for exploration of biorelevant chemical space between small molecules and biologics. However, in comparison with the design and synthesis of small molecules, chemists’ ability to fine-tune the three-dimensional structures and properties of cyclic peptides lag far behind. Intrigued by cyclophane peptide natural products, we wondered whether the rigid, planar, and hydrophobic cyclophane motif could provide a new design element for the synthesis of cyclic peptides with well-behaved 3D structures. Herein, we report a generally applicable method for synthesis of natural-product-like cyclophane-braced peptide macrocycles via Pd-catalyzed intramolecular C(sp3)-H arylation with aryl iodides at the remote gammaposition of various N-terminal aliphatic amino acid units using a simple picolinamide directing group. Products of high structural and stereochemical complexity were quickly assembled from easily accessible peptide precursors prepared by standard solid phase peptide synthesis. Many of these peptide macrocycles show highly ordered structures as revealed by X-ray crystallography. Remarkably, the PA-directed C(sp3)-H cyclization reaction of unprotected peptide substrates carrying various free polar side chains proceeded with high efficiency and selectivity in aqueous media. This demonstrates not only the synthetic utility of Pd-catalyzed C(sp3)-H functionalization reactions, but also offers a valuable new orthogonal reactivity for peptide chemistry.

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

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Allyl boronates are very important reagents in advanced organic synthesis for the allylation of carbonyl compounds[1] and in cross-coupling[2] reactions. A practically unrivalled property of allylboronates is their highly regio- and stereoselective addition to carbonyl compounds to afford homoallylic alcohols.[1a-d, 3] This high selectivity is mainly based on two factors: 1) Allylboronates are configurationally stable, and unlike many allyl metal compounds[4] (such as allyl- Grignard reagents, allyl lithium compounds or allylboranes) do not undergo metallotropic rearrangement and E/Z isomerization at ambient conditions. 2) The six-membered ring transition state (TS) of the allylboration of carbonyl compounds is highly conformationally constrained, which leads to a strong differentiation in the stereoselection process.[3a, 5] Method development for broadening the number of accessible functionalized allyl boronates is one of the most important challenges in organoboron chemistry.

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

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Subnanocatalysts (SNCs) containing various noble metals (Cu, Ru, Rh, Pd, or Pt) with sizes of approximately 1 nm were synthesized using dendritic poly(phenylazomethine)s as a macromolecular template. These materials exhibit high catalytic performance during toluene oxidation without the use of harmful solvents or explosive oxidants, resulting in the formation of valuable organic products, including benzoic acid as the major product. In particular, Pt19 SNC with a narrow particle size distribution exhibits extraordinary catalytic activity, with a turnover frequency of 3238 atom?1 h?1, which is 1700 times greater than that obtained by commercial Pt/C catalysts.

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

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Molecular recognition continues to be an area of keen interest for supramolecular chemists. The investigated [M(L)2]2+ metallo-ligands (M=PdII, PtII, L=2-(1-(pyridine-4-methyl)-1 H-1,2,3-triazol-4-yl)pyridine) form a planar cationic panel with vacant pyridyl binding sites. They interact with planar neutral aromatic guests through pi?pi and/or metallophilic interactions. In some cases, the metallo-ligands also interacted in the solid state with AgI either through coordination to the pendant pyridyl arms, or through metal?metal interactions, forming coordination polymers. We have therefore developed a system that reliably recognises a planar electron-rich guest in solution and in the solid state, and shows the potential to link the resultant host?guest adducts into extended solid-state structures. The facile synthesis and ready functionalisation of 2-pyridyl-1,2,3-triazole ligands through copper(I)-catalyzed azide?alkyne cycloaddition (CuAAC) ?click? chemistry should allow for ready tuning of the electronic properties of adducts formed from these systems.

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