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Metallosupramolecular systems are promising new tools for pharmaceutical applications. Thus, novel self-assembled Pd(ii) coordination cages were synthesized which were exo-functionalized with naphthalene or anthracene groups with the aim to image their fate in cells. The cages were also investigated for their anticancer properties in human lung and ovarian cancer cell lines in vitro. While the observed cytotoxic effects hold promise and the cages resulted to be more effective than cisplatin in both cell lines, fluorescence emission properties were scarce. Therefore, using TD-DFT calculations, fluorescence quenching observed in the naphthalene-based system could be ascribed to a lower probability of a HOMO-LUMO excitation and an emission wavelength outside the visible region. Overall, the reported Pd2L4 cages provide new insights into the chemical-physical properties of this family of supramolecular coordination complexes whose understanding is necessary to achieve their applications in various fields.

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

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Achieving chemo- and regioselectivity simultaneously is challenging in organic synthesis. Transition metal-catalyzed reactions are effective in addressing this problem by the diverse ligand effect on the catalyst center. Ligand-controlled regioselective Pd-catalyzed carbonylation of styrenes with aminophenols was realized, chemoselectively affording amides. Using a combination of boronic acid and 5-chlorosalicylic acid as the additives, linear amides were obtained in high yields and selectivity using tris(4-methoxyphenyl)phosphine (L3) in acetonitrile, while branched amides were obtained in high yields and selectivity in butanone by changing the ligand to 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phenyl-6-phosphaadamantane (L5). Further studies show that the nature of the ligand is key to the regioselectivity. Cone angle and Tolman electronic parameter (TEP) have been correlated to the reactivity and regioselectivity. Studies on the acid additives show that different acids act as the proton source and the corresponding counterion can help enhance the reactivity and selectivity.

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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 inverse 2-pyridyl-1,2,3-triazole “click” ligands, 2-(4-phenyl-1H-1,2,3-triazol-1-yl)pyridine and 2-(4-benzyl-1H-1,2,3-triazol-1-yl)pyridine, and their palladium(II), platinum(II), rhenium(I), and ruthenium(II) complexes have been synthesized in good to excellent yields. The properties of these inverse “click” complexes have been compared to the isomeric regular compounds using a variety of techniques. X-ray crystallographic analysis shows that the regular and inverse complexes are structurally very similar. However, the chemical and physical properties of the isomers are quite different. Ligand exchange studies and density functional theory (DFT) calculations indicate that metal complexes of the regular 2-(1-R-1H-1,2,3-triazol-4-yl)pyridine (R = phenyl, benzyl) ligands are more stable than those formed with the inverse 2-(4-R-1H-1,2,3-triazol-1-yl)pyridine (R = phenyl, benzyl) “click” chelators. Additionally, the bis-2,2?-bipyridine (bpy) ruthenium(II) complexes of the “click” chelators have been shown to have short excited state lifetimes, which in the inverse triazole case, resulted in ejection of the 2-pyridyl-1,2,3-triazole ligand from the complex. Under identical conditions, the isomeric regular 2-pyridyl-1,2,3-triazole ruthenium(II) bpy complexes are photochemically inert. The absorption spectra of the inverse rhenium(I) and platinum(II) complexes are red-shifted compared to the regular compounds. It is shown that conjugation between the substituent group R and triazolyl unit has a negligible effect on the photophysical properties of the complexes. The inverse rhenium(I) complexes have large Stokes shifts, long metal-to-ligand charge transfer (MLCT) excited state lifetimes, and respectable quantum yields which are relatively solvent insensitive.

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

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1,3-Diazetidinones are obtained by bis(dibenzylideneacetone) palladium(O)-catalyzed carbonylation of diaziridines having one substituent attached to the ring carbon atom. This regiospecific insertion into the nitrogen-nitrogen bond also occurs for 3,3-disubstituted diaziridines, provided one uses stoichiometric quantities of cobalt carbonyl.

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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 new complexes have been synthesized from reactions of [M(NCCH3)4][BF4]2 (M = Pd, Pt) with the mixed donor ligand tris(2,4,6-trimethoxyphenyl) phosphine (TMPP). Reaction of [Pd(NCCH3)4][BF4]2 with two equivalents of TMPP in acetone produces the ether-phosphine complex [Pd(TMPP)2][BF4]2, 1. In this molecule the Pd atom is situated at the center of a pseudo-octahedron, with the phosphorus atoms in a cis orientation. The complex was also characterized by infrared, electronic, and NMR spectroscopies as well as by cyclic voltammetry. Reaction of [Pd(NCCH3)4][BF4]2 with four equivalents of TMPP in acetone yields the neutral phosphino-phenoxide compound Pd(TMPP-O)2, 2, where TMPP-O is the demethylated form of TMPP. 1H and 31P{1H} NMR studies of 2 support the assignment of a solution structure that involves free rotation of the uncoordinated phenyl rings of the TMPP ligands. Reaction of [Pt(NCCH3)4][BF4]2 with two equivalents of TMPP in acetonitrile yields [PT(NCCH3)2(TMPP)2][BF4] 2, 3. Structural and spectroscopic data for 3 indicate that free rotation of the arene rings in solution is restricted due to steric influences of the two CH3CN co-ligands. Reaction of PtCl2(NCCH3)2 with two equivalents of TMPP in acetone or reaction of [Pt(NCCH3)4][BF4]2 with four equivalents of TMPP in acetone gives Pt(TMPP-O)2, 4. Reaction of PtCl2(NCCH3)2 with two equivalents of TMPP in tetrahydrofuran yields the neutral compound PtCl(TMPP)(TMPP-O), 5. Although suitable single crystals were not obtained, the structure of compound 5 was deduced from infrared and NMR spectroscopies to be a square planar molecule with one neutral TMPP ligand coordinated in an eta1 fashion and a demethylated TMPP group bound as an eta2-P,O ligand where the phosphorus atoms are trans and the other two coordination sites are occupied by a phenoxide oxygen and a Cl atom.

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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 reaction of 2 with NHR2 (R = Et or Pri) and carbon dioxide in toluene led to the dialkylcarbamato complexes .The derivative trans- was studied by X-ray diffraction methods.The square-planar geometry of the palladium atom involves one oxygen atom of each monodentate carbamato group and two amine nitrogen atoms.An intramolecular N-H…O bond is probably responsible for a further stabilization within the molecule, for the features of the IR bands associated with the carbamato ligand and for the 1H NMR non-equivalence observed within the amine alkyl group at room temperature.

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

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Mononuclear phosphine sulfide Pd(0) complexes and a polymer-supported triphenylphosphine sulfide Pd(0) complex were prepared as new air-stable Pd(0) catalysts for C-C coupling reactions. The phosphine sulfide Pd(0) complexes are not decomposed after completion of Suzuki-Miyaura coupling, and the polymer-supported Pd(0) catalyst is practically recyclable, while phosphine Pd(0) complexes are decomposed into inactive Pd(0) black after consuming the substrates. New catalytic activity of Pd(0) that promotes chalcogen atom replacement of phosphine chalcogenides (R3P=X, X = O, S, Se) is reported. A mechanistic study revealed that the new catalytic chalcogen replacement results from activation of the P=X bond as well as promotion of the oxidative chalcogenide formation. The intermediate phosphine was successfully trapped as a phosphine Pd(II) complex, and the P=X bond activation is applicable to regeneration of phosphine or phosphine sulfide from oxidized phosphine.

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

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Multicavity [Pdn(L)4]2n+ metallosupramolecular cages based on long backboned ligands are an attractive approach to increasing molecular size without loss of the binding specificity conferred by small cavity [Pd2(L)4]4+ assemblies. We herein report the synthesis of two double cavity polypyridyl [Pd3(L)4]6+ cages that bind cisplatin [Pt(NH3)2Cl2] within their internal cavities and interact with triflate (TfO-) on their exohedral faces. We also report the first example of a triple cavity [Pd4(L)4]8+ cage. This cage differs in that the central cavity is phenyl-linked rather than having the pyridyl core as in the peripheral cavities. The difference in cavity character results in selective guest binding of cisplatin in the peripheral cavities, with triflate binding within the central cavity and on the exohedral faces of the peripheral palladium(II) ions. All the cavities could be simultaneously filled by introducing both cisplatin and triflate concurrently, providing the first example of a discrete metallosupramolecular architecture with segregated guest binding in different designed internal cavities. The ligands and cages were characterized by NMR spectroscopy, mass spectrometry, elemental analysis, and, in one case, X-ray crystallography.

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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 novel fluoroaryl-substituted PCP ligand has been synthesized and used to generate the corresponding Pd complexes. The bonding of the fluoroaryl phosphine has been investigated by X-ray crystallography, NMR spectroscopy, and a competition experiment, which indicate that the ligand is sterically comparable to its well-known phenyl analogue but clearly imparts significant electronic differences to the metal center.

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

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We report the synthesis of air-stable Pd(i) dimer complexes featuring biaryl phosphine ligands. Catalytic experiments suggest that these complexes are competent precatalysts that can mediate cross-coupling amination reactions between aryl halides with both aliphatic and aromatic amine nucleophiles. This work represents an expansion of the air-stable precatalyst toolbox for Pd-catalyzed cross-coupling transformations.

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