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A rigid S-functionalized metalloligand is used to pair Janus Au-coated silica microspheres and the resulting assemblies are assessed with optical microscopy. New Pd complexes provide stable molecular interconnects, and the metal centre controls the structure of the linker and provides the desired rigidity, by virtue of its well-established coordination 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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This work demonstrates a new nonconventional ligand design, imidazole/pyridine-based nonsymmetrical ditopic ligands (1 and 1S), to construct a dynamic open coordination cage from nonsymmetrical building blocks. Upon complex formation with Pd2+ at a 1:4 molar ratio, 1 and 1S initially form mononuclear PdL4 complexes (Pd2+(1)4 and Pd2+(1S)4) without formation of a cage. The PdL4 complexes undergo a stoichiometrically controlled structural transition to Pd2L4 open cages ((Pd2+)2(1)4 and (Pd2+)2(1S)4) capable of anion binding, leading to turn-on anion binding. The structural transitions between the Pd2L4 open cage and the PdL4 complex are reversible. Thus, stoichiometric addition (2 equiv) of free 1S to the (Pd2+)2(1S)4 open cage holding a guest anion ((Pd2+)2(1S)4?G?) enables the structural transition to the Pd2+(1S)4 complex, which does not have a cage and thus causes the release of the guest anion (Pd2+(1S)4+G?).

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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 plane parallel arrangement and enhancement of NLO-activity are observed upon coordination of heteroditopic dipoles containing a phosphole ring on square-planar d8-palladium centre.

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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(II) has been used as a gathering and threading metal centre, using a terpy-incorporating ring and a string-like compound containing a monodentate ligand (pyridine derivative). Preliminary experiments show that the fourth ligand of the square planar complex can be exchanged (pyridine-based ligand/aliphatic amine) by modifying the H+ concentration of the medium, allowing us to envision new molecular machines set in motion by protonation/deprotonation.

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

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There is emerging interest in the anti-proliferative effects of metallosupramolecular systems due to the different size and shape of these metallo-architectures compared to traditional small molecule drugs. Palladium(ii)-containing systems are the most abundant class of metallosupramolecular complexes, yet their biological activity has hardly been examined. Here a small series of [Pd2(L)4](BF4)4 quadruply-stranded, dipalladium(ii) architectures were screened for their cytotoxic effects against three cancer cell lines and one non-malignant line. The helicates exhibited a range of cytotoxic properties, with the most cytotoxic complex [Pd2(hextrz)4](BF4)4 possessing low micromolar IC50 values against all of the cell lines tested, while the other helicates displayed moderate or no cytotoxicity. Against the MDA-MB-231 cell line, which is resistant to platinum-based drugs, [Pd2(hextrz)4](BF4)4 was 7-fold more active than cisplatin. Preliminary mechanistic studies indicate that the [Pd2(hextrz)4](BF4)4 helicate does not induce cell death in the same way as clinically used metal complexes such as cisplatin. Rather than interacting with DNA, the helicate appears to disrupt the cell membrane. These studies represent the first biological characterisation of quadruply-stranded helicate architectures, and provide insight into the design requirements for the development of biologically active and stable palladium(ii)-containing metallosupramolecular architectures.

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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 synthesis and X-ray crystal structure of aneN2S)>(BF4)2 (py2<9>aneN2S = 1-thia-4,7-bis(pyridylmethyl)diazacyclononane)(P21/n, a = 10.233(4) Angstroem, b = 11.484(5) Angstroem, c = 19.913(6) Angstroem, beta = 94.03(4) deg, V = 2334(2) Angstroem3, R = 0.0705, Rw = 0.0759) are presented.The crystal structure indicates a long range interaction (2.92 Angstroem) between the planar palladium and the apical sulphur atom.Although this distance is longer than the value for Pd-S bond observed normally there is evidence for a net positive interaction provided by the solution structure as determined by NMR spectroscopy.Comparative analysis of the structural features exhibited by this complex with similar nine-membered chelating ligands emphasizes the presence of an axial Pd-S bond.

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

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Recently, alkyne complexes with terminal thiolate/amide substitution have been shown to act as S,N-chelate ligands in dinuclear complexes. In this study, the detailed synthesis and reactivity of W(II) alkyne complexes bearing different amino groups in the alpha-position are reported. The preparative scheme starts with cationic alkyne complexes [Tp?W(CO)2-I?2-C,C?-C2Br(SR)]PF6 {Tp? = hydridotris(3,5-dimethylpyrazolyl)borate, R = benzyl (Bn), C2H4SiMe3}, which are obtained by applying free bromo alkynes. Subsequent nucleophilic substitution of the bromine substituent led to unsymmetrical substituted alkyne complexes [Tp?W(CO)2-I?2-C,C?-C2(SR)(NHBn)]PF6 with S,N substitution in the alpha position of the coordinated alkyne. Depending on the base used, deprotonation of the secondary amine resulted in either neutral iminoketenyl complexes [Tp?W(CO)2-I?2-C,C?-C2(SR)(NBn)] or a zwitterionic PF5 adduct. Reductive removal of the benzyl protective group was primarily observed at the imine substituent, causing a side-on/end-on rearrangement to the cyanide substituted carbene complex K[Tp?W(CO)2-I?1-C(CN)(SBn)]. The reversibility of the rearrangement was proven with HBF4/Et2O, because double protonation led to [Tp?W(CO)2-I?2-C,C?-C2(SR)(NH2)]BF4 exhibiting an unprecedented primary amine substitution at the coordinated alkyne. The reaction sequence starting with the thiol SC2H4SiMe3 derivative leading to the desired [Tp?W(CO)2-I?2-C,C?-C2S(NHBn)] with a terminal S atom as well as the bonding situation in those complexes is discussed based on full spectroscopic characterization including X-ray structure analyses. Finally, a trinuclear complex assembled by homoleptic coordination of Pd(II) by two anionic S,N-chelates [Tp?W(CO)2-I?2-C,C?-C2S(NBn)]- 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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A tris(phosphine) ligand with a triarylbenzene backbone was employed to support mono-nickel(II) and -palladium(II) complexes. Two phosphine arms coordinated to the metal center, while the third phosphine was found to form a C-P bond with dearomatization of the central arene. Deprotonation effected the rearomatization of the central ring and metal reduction from M(II) to M(0). The overall conversion corresponds to a functionalization of an unactivated arene C-H bond to a C-P bond. This transformation represents a rare type of mechanism of C-H functionalization, facilitated by the interactions of the group 10 metal with the arene pi system. This conversion is reminiscent of and expands the scope of recently reported intramolecular rearrangements of biaryl phosphine ligands common in group 10 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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Metalloreceptors 1a and 1b were synthesized by palladation of 42- and 54-membered crown ethers that have two SCS-pincer ligand moieties. The X-ray crystallographic analysis reveals that the metalloreceptor 1b has a folded structure in which the two pincer-Pd moieties are stacked in a parallel manner. The metalloreceptor 1b recognizes the aromatic bidentate guests 4,4?-bipyridine, pyrazine, and pyrimidine and binds to them in a bridging fashion to form the corresponding bimacrocyclic 1:1 complex. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

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

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Establishment of a general one-pot cascade reaction protocol would dramatically reduce the effort of multistep organic synthesis. We demonstrate that the unique structure of M12L24 self-assembled complexes gives them the potential to serve as catalyst carriers for enabling continuous chemical transformations. A stereoselective cascade reaction (allylic oxidation followed by Diels-Alder cyclization) with two intrinsically incompatible catalysts was demonstrated. Our system is advantageous in terms of availability, scalability, and predictability.

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