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The synthesis of the new bis[2-(diphenylphosphino)ethyl](hydroxymethyl)phosphine tridentate ligand LCH2OH/Ph is reported. The ligand reacts with [Pd(Cl)2(PhCN)2] to form [Pd(LCH2OH/Ph)Cl]Cl. Exchange of the chloride ions for triflate (OTf-) using AgOTf yielded pure [Pd(LCH2OH/Ph)OTf]OTf. In addition to spectral characterization, the free ligand, LCH2OH/Ph, and the PdII complex, [Pd(LCH2OH/Ph)OTf]OTf, were structurally characterized. The synthesis of the Triphos ligand derivative LCH2OH/Ph is reported, along with the corresponding PdII complex. In addition to spectral characterization of the free ligand and PdII complex, structural characterization is reported for [Pd(LCH2OH/Ph)OTf]OTf.

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

The important role of Tetrakis(acetonitrile)palladium(II) tetrafluoroborate

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Photon-powered charge separation is achieved in a supramolecular architecture based on the dense packing of functional building blocks. Therefore, self-assembled dimers of interpenetrated coordination cages consisting of redoxactive chromophors were synthesized in a single assembly step starting from easily accessible ligands and Pd(II) cations. Two backbones consisting of electron rich phenothiazine (PTZ) and electron deficient anthraquinone (ANQ) were used to assemble either homo-octameric or mixed-ligand double cages. The electrochemical and spectroscopic properties of the pure cages, mixtures of donor and acceptor cages and the mixed-ligand cages were compared by steady-state UV-vis and transient absorption spectroscopy, supported by cyclic voltammetry and spectroelectrochemistry. Only the mixed-ligand cages, allowing close intra-assembly communication between the donors and acceptors, showed the evolution of characteristic PTZ radical cation and ANQ radical anion features upon excitation in the transient spectra. In contrast, excitation of the mixtures of the homo-octameric donor and acceptor cages in solution did not lead to any signs of electron transfer. Densely packed photo- and redox-functional self-assemblies promise molecular-level control over the morphology of the charge separation layer in future photovoltaic applications.

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

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Cationic Pd2+ complexes were used for the preparation of poly(2,3-bicyclo[2.2.1]hept-2-ene), a saturated polymer with the bicyclic structure of the monomer left intact. The polymer was characterized by thermal analyses and molecular weight determinations. Samples with narrow molecular weight distributions (polydispersities Mw/Mn as low as 1.07) were prepared with the initiator [Pd(CH3CN)4] [BF4]2. Polymer chain growth of this addition polymer was found to continue after renewed monomer addition, indicating rare chain transfer and chain termination.

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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 Pd(II)-catalyzed direct selective fluorination reaction of carboranes using a F+ reagent has been developed, leading to a series of polyfluorocarboranes in high isolated yields. The mechanism involving electrophilic B-H activation, oxidation of Pd(II) by F+ species, and reductive elimination is proposed.

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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 previously reported Pd-catalyzed MCR of 4-pentyn-1-ol derivatives with salicylaldehyde and methyl orthoformate follows an unexpected course when carried out with the 5alpha- and 5beta-epimers of 4,5-secocholestan-5-ol, leading to chroman ketals. The homologation of the alkynol and the restriction of its conformational equilibrium trigger a drastically different reaction course.

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

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Self-assembly processes of three octahedron-shaped [Pd6L12]12+ cages were investigated by an NMR-based quantitative approach. As to the on-pathway of the Pd6L12 cage assembly, the final intramolecular ligand exchange in an incomplete cage, [Pd6L12Py?]12+ (Py?: 3-chloropyridine, which was used as a leaving ligand), is the rate-determining step in the self-assembly of all the three [Pd6L12]12+ cages. Contrary to the previous finding that the self-assembly of [PdmL2m]2m+ structures (m = 2, 3) and [Pd6L8]12+ capsules from rigid multitopic ligands efficiently takes place without the formation of kinetically trapped species under mild conditions, in the self-assembly of the [Pd6L12]12+ cages, even relatively rigid ditopic ligands co-produced 100 nm-sized kinetic traps through off-pathways, which would be because the energy landscape becomes more complicated by increasing the number of components in the final assembly. It was found that when Py? was used as a leaving ligand in CD3CN, the [Pd6L12]12+ cages were produced in high yield, preventing the formation of the kinetically trapped species, which indicates that the use of Py? as a leaving ligand in CD3CN is effective to obtain the thermodynamically most stable species.

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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 intrinsic features of (hetero-arene)-metal interactions have been elusive mainly because the systematic structure analysis of non-anchored hetero-arene-metal complexes has been hampered by their labile nature. We report successful isolation and systematic structure analysis of a series of non-anchored indole-palladium(II) complexes. It was revealed that there is a sigma-pi continuum for the indole-metal interaction, while it has been thought that the dominant coordination mode of indole to a metal center is the Wheland-intermediate-type sigma-mode in light of the seemingly strong electron-donating ability of indole. Several factors which affect the sigma- or pi-character of indole-metal interactions are discussed. Continuum split: The isolation and systematic structural analysis of non-anchored indole-palladium(II) complexes revealed that there is a sigma-pi continuum for heteroarene-metal complexes. These findings may provide insights into key catalytic intermediates of metal-catalyzed heteroarene transformations.

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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 rational synthesis strategy leads to tailor-made high-nuclearity cluster complexes comprising discrete Ru-Pd-Ru units (see picture). The transformation of these heterometallic clusters into supported, finely distributed, metal particles of Ru/Pd alloy could lead to interesting applications in catalysis.

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

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Two new bimetallic Pd complexes have been synthesized and characterized and their catalytic activity checked for the aldol reaction of aldehydes with methyl isocyanoacetate. Each palladium atom is coordinated to an SCS-type ligand and the two pincer units are linked by a chiral spacer. The catalytic aldol reaction of methyl isocyanoacetate with aldehydes proceeds quickly but no significant diastereoselectivity and enantioselectivity is found. The comparison with a homologous mononuclear Pd complex shows no differences with the bimetallic compounds, concluding that there is no cooperativity between the metal centers. Two silica-supported catalysts prepared with a bimetallic compound show catalytic activity with very minor enantioselectivity.

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

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Arylations of substituted enamides by aryl iodides were achieved for the first time via an unusual PdCl2(COD)/Ag3PO4 catalytic system. A broad range of (Z)-beta-amido-beta-arylacrylates were prepared regio- and stereoselectively in a highly efficient manner.

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