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We report that 1-(2-picolyl)-1,2,3-triazole (click triazole) forms stable complexes with transition-metal ions in which the coordination involves the triazole N2 nitrogen atom and the pendant 2-picolyl group. This is exemplified by model compound 1-(2-picolyl)-4-phenyl-1H-1,2,3-triazole (Lx) and its complexes with transition-metal ions of PtII, PdII, CuII, RuII, and AgI. The coordination was investigated experimentally and theoretically. Ligand Lx easily reacted at room temperature with cis-[PtCl2(DMSO)2], [Pd(CH3CN)4](BF4)2, CuCl 2, [RuCl(mu-Cl)(?6-p-cymene)]2, and AgNO3 to give stable chelates [PtCl2Lx] (1), [Pd(Lx)2](BF4)2 (2), [CuCl 2(Lx)2] (3), [RuCl(?6-p-cymene) Lx]OTf (4), and [Ag2(Lx)2(NO 3)2] (5), respectively, in 60-98% yield. The structures of 1-5 were unambiguously confirmed by NMR spectroscopy and single-crystal X-ray diffraction analysis. Density functional theory calculations were carried out in order to theoretically investigate the stabilization factors in 1-5. A comparison of the chelating properties of ligand Lx was made with structurally similar and isomeric 1-(2-aminoethyl)-substituted 1,2,3-triazole (Ly) and 4-(2-aminoethyl)-substituted 1,2,3-triazole (Lz). The complexation affinity of Lx was attributed to phi-back-donation from the metal to the pendant pyridine side arm, whereas the stability of the complexes involving Ly and Lz mainly originates from efficient phi-back-donation to the triazole ring.

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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 NHEt2 and carbon dioxide with (BF4)2 at room temperature and atmospheric pressure produced the N-N-diethylcarbamato complex trans-Pd(O2CNEt2)2(NHEt2)2.Single-crystal X-ray diffractometry showed the monodentate carbamato groups and the amine ligands in a planar arrangement of the donor atoms around palladium.Evidence for the formation of the corresponding isopropyl derivative is 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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For the development of novel nanospace with unique electrostatic character, we prepared new capsular and tubular nanostructures by the quantitative assembly of metal ions and bent bisacridinium ligands. The capsule and tube have closed spherical and open cylindrical cavities, respectively, with diameters of around 1 nm surrounded by cationic polyaromatic panels. Thanks to the facile synthetic protocol (three steps), another polycationic capsule with an elliptical nanocavity was also prepared by using an elongated ligand. In spite of the absence of pendant hydrophilic groups, the spherical polyaromatic capsule shows sufficient water solubility due to the polycationic shell. Moreover, the highly cationic cavity (12+) can selectively encapsulate anionic organic compounds in water.

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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 incorporation of dialkyl sulfide side chains in metallodendrimers is a simple method for their insertion into a monolayer of decanethiol formed by self-assembly on a gold surface. The dendrimer binds through the sulfide group to a defect in the monolayer on the gold surface (see picture). The surface concentration of the isolated dendrimer adsorbate can be regulated by the adsorption time (for example, 55 adsorbates on a surface of 200 x 200 nm2 after 20 h).

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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 multi-donor phosphinoferrocene carboxamide, FcCONHCH2CH2PPh2 (1, Fc = ferrocenyl), was prepared, converted into the corresponding phosphine oxide 1O and phosphine selenide 1Se and, mainly, studied as a ligand in Pd(ii) complexes. In its native form, amide 1 preferentially coordinated soft Pd(ii) as a simple phosphine, giving rise to mixtures of cis and trans-[PdX2(1-kappaP)2] (2; X = Cl (a), Br (b), and I (c)), wherein the isomer ratios depended on the auxiliary halide ligand or, alternatively, to the complex [(LNC)PdCl(1-kappaP)] (6, LNC = 2-[(dimethylamino)methyl-kappaN]phenyl-kappaC1). This coordination mode was nevertheless easily changed when creating a vacant coordination site at the palladium. Thus, treatment of 2a with NH4[PF6] in the presence of free 1 produced [PdCl(1-kappaP)3][PF6] (3), while complete halogen removal with a Ag(i) salt led to cationic complexes cis-[Pd(1-kappa2O,P)2]X2 (4, X = CF3SO3 (a), ClO4 (b), BF4 (c)) or [(LNC)Pd(1-kappa2O,P)]X (7a and 7b), containing seven-membered O,P-chelate rings. In contrast, amide nitrogen deprotonation with KOt-Bu followed by spontaneous intramolecular halogen substitution resulted in the transformation of 6 into the chelate complex [(LNC)Pd{(1-H)-kappa2N,P}] (8) featuring a five-membered N,P-chelate ring, and in the conversion of 2a and 2b into the product of C-H bond activation [Pd{Fe(eta5-C5H3CONCH2CH2PPh2-kappa3C,N,P)(eta5-C5H5)}(1-kappaP)] (5), with doubly chelating deprotonated 1. Importantly, complexes 2-4-5 and 6-7-8 were mutually interconverted in triads (by protonation/deprotonation and by halide addition/abstraction), which highlights the flexible coordination and chemical stability of ligand 1. The crystal structures of 1O·H2O, trans-2a·MeCN, trans-2b·3C2H4Cl2, trans-2c·2.5C2H4Cl2, 4a·CH2Cl2, 5·3CHCl3·Et2O, and 8 were determined by single-crystal X-ray diffraction analysis, and the representative compounds were studied by cyclic voltammetry.

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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 ferrocene-containing [Pd2(LFc)4]4+(X-)4 (where X- = BF4- or SbF6-) self-assembled cages (C·BF4 and C·SbF6) were synthesised from the known, rotationally flexible, 1,1?-bis(3-pyridylethynyl)ferrocene ligand (LFc), and characterised by 1H, 13C and diffusion ordered (DOSY) NMR and UV-visible absorption spectroscopies, high resolution electrospray ionisation mass spectrometry (HR-ESI-MS), elemental analysis, X-ray crystallography and cyclic voltammetry (CV). The molecular structures confirmed that cage-like systems (C·BF4 and C·SbF6) were generated. Similar to related [Pd2L4]4+(X-)4, C·SbF6 was able to interact with a range of neutral and anionic guests, with p-toluenesulfonate showing the strongest association constant. Cyclic voltammetry studies revealed that the cage systems were redox active. However, the redox potential of the cage was unperturbed upon the addition of guests.

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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 Cu(I)-catalyzed 1,3-cycloaddition of organic azides with terminal alkynes, the CuAAC “click” reaction is currently receiving considerable attention as a mild, modular method for the generation of functionalized ligand scaffolds. Herein we show that mild one-pot “click” methods can be used to readily and rapidly synthesize a family of functionalized bidentate 2-pyridyl-1,2,3-triazole ligands, containing electrochemically, photochemically, and biologically active functional groups in good to excellent yields (47-94%). The new ligands have been fully characterized by elemental analysis, HR-ESI-MS, IR, 1H and 13C NMR and in three cases by X-ray crystallography. Furthermore we have demonstrated that this family of functionalized “click” ligands readily form bis-bidentate Pd(II) complexes. Solution studies, X-ray crystallography, and density functional theory (DFT) calculations indicate that the Pd(II) complexes formed with the 2-(1-R-1H-1,2,3-triazol-4-yl)pyridine series of ligands are more stable than those formed with the [4-R-1H-1,2,3-triazol-1-yl)methyl]pyridine “click” ligands.

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

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Nanospheres can be formed by combining 24 bispyridinyl building blocks with a palladium or platinum precursor. These spheres can be functionalized on the inside with a gold(I) chloride complex leading to a high local concentration of gold(I) complexes. The high local concentration makes the neutral gold species an active catalyst. Furthermore, the platinum-gold spheres can be post-modified with a silver(I) salt to form cationic gold(I) catalysts. The platinum assemblies are demonstrated to be stable in the presence of various substrates and as a result several cyclization reactions have been carried out using these new spheres as catalysts. Higher conversions in a [4+2] cycloaddition are observed for the sphere catalyst compared to the mono-nuclear analogues. Also the cyclization of 1,6-enynes can be facilitated by the confined gold catalyst and high activity is observed in the activation of allenes. For the lactonization of alkynoic acids, a different selectivity is observed compared to a standard gold(I) complex, demonstrating that the high local concentration due to a confined space can induce other selectivity 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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Photochromic [Pd2L4] coordination cages based on dithienylethene (DTE) ligands L allow triggering guest uptake and release by irradiation with light of different wavelengths. The process involves four consecutive electrocyclic reactions to convert all chromophores between their open and closed photoisomeric forms. So far, guest affinity of the fully switched species was elucidated, but mechanistic details concerning the intermediate steps remained elusive. Now, a new member of the DTE cage family allows unprecedented insight into the interplay between photoisomerization steps and guest location inside/outside the cavity. Therefore, the intrinsic chirality of the DTE backbones was used as reporter for monitoring the fate of a chiral guest. In its “open” photoisomeric form (o-L, [Pd2(o-L)4] = o-C), the C2-symmetric DTE chromophore quickly converts between energetically degenerate P and M helical conformations. After binding homochiral 1R-(-) or 1S-(+) camphor sulfonate (R-CSA or S-CSA), guest-to-host chirality transfer was observed via a circular dichroism (CD) signal for the cage-centered absorption. Irradiating the R/S-CSA@o-C host-guest complexes at 313 nm produced configurationally stable “closed” photoisomers, thus locking the induced chirality with an enantiomeric excess close to 25%. This value (corresponding to chiral induction for one out of four ligands), together with DOSY NMR, ion mobility mass spectrometry, and X-ray structure results, shows that closure of the first photoswitch is sufficient to expel the guest from the cavity.

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

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Carborane cage chirality is an outstanding issue of great interest as the icosahedral carboranes have wide applications in medicinal and materials chemistry. The synthesis of optically active carborane derivatives, whose chirality is associated with the substitution patterns on the polyhedron, will open new avenues to carborane chemistry. We report herein an efficient method to achieve chiral-at-cage arylation of o-carboranes with high regio- and enantioselectivities by a strategy of palladium-catalyzed asymmetric intramolecular B-H arylation and cyclization. This represents the first example of the enantioselective reaction on carboranes, providing an efficient way for the construction of chiral-at-cage compounds with new skeletons.

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