Properties and Exciting Facts About 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex

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Supramolecular assemblies with symmetrical octahedral structures – Synthesis, characterization, and electrochemical properties

Functional nanosized cage complexes with an octahedral framework have been synthesized by the facile self-assembly reactions of six 90 Pd II-containing compounds {[Pd(dppf)(OTf)2] or [Pd(PPh 3)(OTf)2], dppf = 1,1?-bis(diphenylphosphanyl) ferrocene, OTf = trifluoromethylsulfonate} and four 120 functional tritopic ligands [2,4,6-tri(4-pyridyl)-1,3,5-triazine] in acetone. Diffusion-ordered NMR spectroscopy (DOSY) and AFM images clarify the formation of 3-4 nm nanoparticles. These highly symmetrical cage complexes are discrete, face-directed, functional nanoparticles with symmetrical octahedral structures. The self-assembled functional cage complexes exhibit interesting electrochemical activities, and thus will potentially be useful in the catalysis of redox reactions, the encapsulation of sizeable guest molecules and the control of organic synthetic reactions. The appropriate stoichiometric combination of 90 PdII-containing units with 120 tritopic units affords octahedral symmetrical nanocages through covalently linked functional groups, which exhibit interesting electrochemical activities. Copyright

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

Awesome and Easy Science Experiments about 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex

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Synthesis and near infrared electrochromic properties of metallodithiolene complexes

Four metallodithiolene complexes [4,8-bis(octyloxy)-1,3,5,7-tetrathia]?di[1,1?-bis(diphenylphosphino)ferrocene?palladium(II)] (3), [4,8-bis(octyloxy)-1,3,5,7-tetrathia]di[1,3-bis(diphenylphosphino)propane?nickel(II)] (4), [4,8-bis(octyloxy)-1,3,5,7-tetrathia] ?[1,1?-bis(diphenylphosphino)ferrocene?palladium(II)]?[1,3-bis(diphenylphosphino)propane·nickel(II)] (5) and di[4,8-bis (octyloxy)-1,3,5,7-tetrathia]?[1,1?-bis(diphenylphosphino)ferrocene?palladium(II)]?nickel(II) (6) were synthesized and the near-infrared (NIR) electrochromic properties were studied. The spectroelectrochemical spectra and the electrochromic parameters such as optical contrast, switching time, optical density change, electrochromic efficiency and optical attenuation of complexes 3?6 were investigated in detail. The symmetric binuclear complex 4 showed relatively high electrochromic efficiency of 63.0 and 75.4 cm2/C both in the two oxidation states. The complexes exhibited excellent electroactive/electrochromic stability characterized by chronoamperometry (>4000 cyclic switches).

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

The important role of 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex

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Discovery of biphenyl-aryl ureas as novel VEGFR-2 inhibitors. Part 4: Exploration of diverse hinge-binding fragments

Abstract VEGFR-2 plays an essential role in angiogenesis and is an important target for cancer therapy. A series of biphenyl-aryl ureas were synthesized and evaluated as novel VEGFR-2 inhibitors. The pyridine, methylamine carbonyl pyridine and pivaloyl amide pyridine were introduced as novel hinge binding fragment. The majority of title compounds displayed potent VEGFR-2 inhibition. In particular, L1, L9, W14 and W15 exhibited significant enzymatic inhibitory activity with IC50 values of 0.36 nM, 0.22 nM, 0.15 nM and 0.14 nM. Compounds L1, L9 and W15 displayed potent antiproliferative activity against A549 and SMMC-7721 cells. SAR study suggested that incorporation of 3-trifluoromethyl and methylamine carbonyl on terminal pyridine could improve VEGFR-2 inhibitory activity. Molecular docking illustrated that urea moiety formed two critical hydrogen bonds with the DFG residues of VEGFR-2. The results indicated that these biphenyl-aryl ureas could serve as promising lead compounds for further optimization.

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

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Stereoselective Synthesis of (Z)-(1-Organo-1-alkenyl)boronic Esters by the Palladium-Catalyzed Cross-Coupling Reaction of (Z)-(1-Iodo-1-alkenyl)boronic Esters with Organozinc Reagents

The cross-coupling reaction of organozinc reagents with a pinacol ester of (Z)-(1-iodo-1-hexenyl)boronic acid in the presence of Pd(PPh3)4 proceeded with complete retention of the configuration of the starting boronate.The reaction provided (E)-(1-organo-1-hexenyl)boronic esters which were not available by the conventional hydroboration technique.The utility of the reaction was demonstrated by stereoselective synthesis of an exocyclic alkene via the cross-coupling reaction with chloroenone.

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

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[3+3] Cyclocondensation of Disubstituted Biphenyl Dialdehydes: Access to Inherently Luminescent and Optically Active Hexa-substituted C3-Symmetric and Asymmetric Trianglimine Macrocycles

A general synthetic route to inherently luminescent and optically active 6-fold substituted C3-symmetric and asymmetric biphenyl-based trianglimines has been developed. The synthesis of these hexa-substituted triangular macrocycles takes advantage of a convenient method for the synthesis of symmetrically and asymmetrically difunctionalized biphenyl dialdehydes through a convergent two-step aromatic nucleophilic substitution-one-pot Suzuki-coupling reaction protocol. A modular [3+3] diamine-dialdehyde cyclocondensation reaction between both the symmetrically and asymmetrically difunctionalized-4,4?-biphenyldialdehydes with enantiomerically pure (1R,2R)-1,2-diaminocyclohexane was employed to construct the hexa-substituted triangular macrocycles. B97-D/6-311G(2d,p) density functional theory determined structures and X-ray crystallographic analysis reveal that the six substituents appended to the biphenyl legs of the trianglimine macrocycles adopt an alternating conformation not unlike the 1,3,5-alternate conformation observed for calix[6]arenes. Reduction of the imine bonds using NaBH4 afforded the corresponding 6-fold substituted trianglamine without the need to alkylate the amine nitrogen atoms which could hinder their later use as metal coordination sites and without having to introduce asymmetric carbons.

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

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Synthesis of functionalized thiophenes and oligothiophenes by selective and iterative cross-coupling reactions using indium organometallics

The synthesis of unsymmetrical 2,5-disubstituted thiophenes by selective and sequential palladium-catalyzed cross-coupling reactions of indium organometallics with 2,5-dibromothiophene is reported. Following an iterative coupling sequence, alpha-oligothiophenes were synthesized in good yields and with high atom economy.

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

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Facile synthesis of beta-derivatized porphyrins – Structural characterization of a beta – beta-bis-porphyrin

A generally applicable Suzuki methodology for the synthesis of beta- derivatized porphyrins has been developed starting from bromoporphyrin 1, which is converted into an air- and water-stable boronate derivative. Metal- mediated cross-coupling of the latter compound with various aryl bromides furnishes beta-arylporphyrins 2 with yields similar to those reported for derivatization at the meso-position. The utility of the method was demonstrated with the preparation and structural characterization of bis- porphyrin 3, directly linked at the beta-positions of the rings.

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

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Boryltrihydroborate: Synthesis, structure, and reactivity as a reductant in ionic, organometallic, and radical reactions

Reaction of lithium 1,3-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2- diazaborol-2-ide with borane·THF provides the first boryl-substituted borohydride: lithium [1,3-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2- diazaborol-2-yl]trihydroborate. The compound is fully characterized by 11B, 1H, and 7Li NMR spectra and other means, and these data are compared to neutral and anionic benchmark compounds. The compound crystallizes as a dimer complexed to four THF molecules. The dimer lacks the bridging B-H bonds seen in neutral boranes and is instead held together by ionic Li – -HB interactions. A preliminary scan of reactions with several iodides shows that the compound participates in an ionic reduction (with a primary-alkyl iodide), an organometallic reduction (Pd-catalyzed with an aryl iodide), and a radical reduction (AIBN-initiated with a sugar-derived iodide). Accordingly the new borylborohydride class may share properties of both traditional borohydrides and isoelectronic N-heterocyclic carbene boranes.

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

Extracurricular laboratory:new discovery of 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex

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Synthesis, crystal structure, and conjugation properties of phenanthroline copper phosphine complexes

Facial synthetic method of 4,7-position conjugation extended phenanthrolines and X-ray structure of copper phosphine phenanthroline complexe were reported. The crystal structures showed pi-stacking and hydrogen bonding, and a small torsional angle between phen and phenylacetylene. These complexes exhibited strong conjugation dependant MLCT luminescence. The electronic and fluorescence spectra displayed a gradual red shift of the MLCT band as the conjugation increased. The presence of the phenyl groups reduced the energy of the pi? state in the d-pi? MLCT transition, allowing for the red shift. The electron-donating tri-isopropylsilyl (TIPS) groups on the ethynyl moiety increased the energy of the MLCT charge vector, allowing for the blue shift at the luminescence.

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

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Quantitative formation of [2]catenanes using copper(I) and palladium(II) as templating and assembling centers: The entwining route and the threading approach

Transition metal-mediated templating and self-assembly have shown powerful potentials for the synthesis of interlocked molecules. These two strategies were combined in designing and preparing a new type of coordination catenanes incorporating Cu(I) and Pd(II) metal centers. The ligand designed here contains a phenanthroline core and pyridine sidearms (compound 1). Using this phenanthroline-pyridine conjugated ligand, two approaches were examined, which were shown to be surprisingly efficient for the catenane synthesis: the entwining route (entwining of two ligands around Cu(I) followed by Pd(II) clipping) and the threading approach (Cu(I)-templated threading of a cyclic ligand on an acyclic ligand followed by the PD(II) clipping of the second ring). In the former method, stepwise treatment of 1 with Cu(CH3CN)4PF6 (templating center) and enPd(NO3)2 (assembling center) gives rise to the quantitative formation of CuPd2 catenane 18. In the latter method, Cu(I) templates the threading of phenanthroline-containing macrocycle 2 on ligand 1, which is followed by Pd(II) clipping to give hetero catenane 20. In both approaches, the formation of catenanes is convincing thanks to the strong templating effect of Cu(I), while the ring closure steps are efficiently furnished by Pd(II)-directed self-assembly.

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