Awesome and Easy Science Experiments about [1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium(II)

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Kumada – Corriu coupling of Grignard reagents, probed with a chiral Grignard reagent

The Grignard reagent 2, in which the magnesium-bearing carbon atom is the sole stereogenic centre has been coupled with vinyl bromide under Pd(0) or Ni(0)-catalysis to give compound 3 with full retention of configuration. Coupling using Fe(acac)3 or Co(acac)2 as catalyst was accompanied by considerable racemisation. These findings are discussed with respect to a dichotomy between concerted polar and stepwise SET transmetallation pathways.

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

Can You Really Do Chemisty Experiments About Pd2(DBA)3

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Accessing 2-(hetero)arylmethyl-, -allyl-, and -propargyl-2,1-borazaronaphthalenes: Palladium-catalyzed cross-couplings of 2-(Chloromethyl)-2,1-borazaronaphthalenes

The synthesis of 2-(chloromethyl)-2,1-borazaronaphthalene has provided an opportunity to expand dramatically the functionalization of the azaborines. This azaborinyl building block can serve as the electrophile in palladium-catalyzed cross-coupling reactions to form sp3-sp and sp3-sp2 bonds. The cross-coupling reactions of 2-(chloromethyl)-2,1-borazaronaphthalene with potassium (hetero)aryl- and alkenyltrifluoroborates as well as terminal alkynes provides access to a variety of novel azaborines, allowing a library of pseudobenzylic substituted azaborines to be prepared from one common starting material.

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

Simple exploration of 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex

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Synthesis of dendritic metalloporphyrins with distal H-bond donors as model systems for hemoglobin

We report the synthesis of the first- (G1) and second-generation (G2) dendritic FeII porphyrins 1-Fe-4-Fe (G1) and 6 ¡¤ Fe (G2) bearing distal H-bond donors ideally positioned for stabilization of Fe II-O2 adducts by H-bonding (Fig. 1). A first approach towards the construction of these novel biomimetic systems failed unexpectedly: the Suzuki cross-coupling between appropriately functionalized ZnII porphyrins and orthoethynylated aryl derivatives, serving as anchors for the distal H-bond donor moieties, was unsuccessful (Schemes 1, 3, and 5), presumably due to steric hindrance resulting from unfavorable coordination of the ethynyl residue to the Pd species in the catalytic cycle (Scheme 6). The target molecules were finally prepared by a route in which the ortho-ethynylated meso-aryl ring is introduced during porphyrin construction in a mixed condensation involving the two dipyrrylmethanes 33 and 34, and aldehyde 36 (Schemes 7 and 8). Following attachment of the dendrons (Scheme 11), the distal H-bond donors were introduced by Sonogashira cross-coupling (Scheme 12), and subsequent metallation afforded the dendritic FeII porphyrins 1 ¡¤ Fe-6 ¡¤ Fe. 1H-NMR Spectroscopy proved the location of the H-bond donor moiety atop the porphyrin surface, and X-ray crystal-structure analysis of model system 45 (Fig. 2} revealed that this moiety would not sterically interfere with gas binding. With 1,2-dimethyl-1H-imidazole (DiMeIm) as ligand, the dendritic FeII porphyrins formed five-coordinate high-spin complexes (Figs. 3 and 4) and addition of CO led reversibly to the corresponding stable six-coordinate gas complexes (Fig. 6). Oxygenation, however, did not result in defined FeII-O2 complexes as rapid decomposition to FeIII species took place immediately, even in the case of the G2 dendrimer 6¡¤Fe(DiMeIm) (Fig. 7). In contrast, stable gas adducts are formed between dendritic CoII porphyrins and O 2 in the presence of DiMeIm as axial ligand, as revealed by electron paramagnetic resonance (EPR). The possible stabilization of these complexes through H-bonding involving the distal ligand is currently under investigation in multidimensional and multifrequency pulse EPR experiments.

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

Extracurricular laboratory:new discovery of 52409-22-0

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D-A Polymer with a Donor Backbone – Acceptor-side-chain Structure for Organic Solar Cells

We report the design, synthesis, and properties of a novel type of donor (D)-acceptor (A) polymer, poly(3-(([2,2?:5?,2??-terthiophen]-3-yl-5,5?-diyl)methylene)-1-(2-octyldodecyl)indolin-2-one) (PTIBT), with a donor backbone and acceptor side chains (Type II D-A polymer) as donor for organic solar cells (OSCs) as opposed to the conventional D-A polymers having both donor and acceptor units on backbone (Type I D-A polymers). PTIBT having a backbone consisting of thiophene donor units and side chains containing indolin-2-one acceptor units was synthesized very conveniently in three steps. This polymer has a high dielectric constant of 7.70, which is beneficial for the exciton diffusion and dissociation in the active blend layer in an OSC. In addition, PTIBT was found to have a low-lying HOMO energy level of ?5.41 eV and a wide band gap of 1.80 eV in comparison to its counterpart Type I D-A polymer. In organic thin film transistors (OTFTs), PTIBT showed typical p-type semiconductor performance with hole mobilities of up to 1.81¡Á10?2 cm2 V?1 s?1. When PTIBT and ITIC were used as donor and acceptor to form a blend active layer, the best OSC device showed a JSC of 15.19 mAcm?2, a VOC of 0.66 V, and a fill factor of 0.57, resulting in a power conversion efficiency (PCE) of up to 5.72%.

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

Archives for Chemistry Experiments of 52409-22-0

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Platelet ADP receptor inhibitors

Novel compounds of formulae (I) to (VIII), which more particularly include sulfonylurea derivatives, sulfonylthiourea derivatives, sulfonylguanidine derivatives, sulfonylcyanoguanidine derivatives, thioacylsulfonamide derivatives, and acylsulfonamide derivatives which are effective platelet ADP receptor inhibitors. These derivatives may be used in various pharmaceutical compositions, and are particularly effective for the prevention and/or treatment of cardiovascular diseases, particularly those diseases related to thrombosis. The invention also relates to a method for preventing or treating thrombosis in a mammal comprising the step of administering a therapeutically effective amount of a compound of formulae (I) to (VIII), or a pharmaceutically acceptable salt thereof.

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

Discovery of Pd2(DBA)3

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Enantioselective Pd-catalyzed decarboxylative allylic alkylation of thiopyranones. Access to acyclic, stereogenic alpha-quaternary ketones

A catalytic, enantioselective decarboxylative allylic alkylation of 4-thiopyranones is reported. The alpha- quaternary 4-thiopyranones produced are challenging to access by standard enolate alkylation owing to facile ring-opening beta- sulfur elimination. In addition, reduction of the carbon-sulfur bonds provides access to elusive acyclic alpha-quaternary ketones. The alkylated products are obtained in up to 92% yield and 94% enantiomeric excess.

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

Discovery of 32005-36-0

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Synthesis and structure of eta2-phosphonioalkene-palladium(0) complexes. A catalyst intermediate in the palladium-mediated synthesis of alkenylphosphonium halides

Treatment of Pd(PPh3)4 with PhCH=CHBr in THF at 45C gave [(trans-PhCH=CHPPh3)Pd(PPh3)2] +Br- (1), which was found to be converted from Pd(PPh3)2-(CH=CHPh)Br. X-ray structural analysis shows that 1 adopts a distorted-square-planar geometry with two PPh3 ligands and a (PhCH=CHPPh3)+ moiety. The C-C double bond in the latter is pi-bonded to the palladium(0) center and occupies two of the four square-planar coordination sites. Under similar reaction conditions, {Pd[trans-PhCH=CHP(p-tolyl)3][P(p-tolyl)3] 2}+Br- (2) was formed from Pd[P(p-tolyl)3]4 and PhCH=CHBr, while [(trans-MeCH=CHPPh3)Pd(PPh3)2] +Br- (3) was isolated from the reactions of Pd(PPh3)4 with MeCH=CHBr. Treating PhCH=CHBr with trans-Pd(PPh3)2(C6H4O-p-CH 3)I in THF at ambient temperature led to the formation of (trans-PhCH=CHPPh3)Pd(PPh3)X (5) and (p-CH3OC6H4PPh3)+X – (X, mixture of Br and I). Complex 5 (X = Br) can be prepared by treating trans-PhCH=CH(PPh3)+Br- with Pd(dba)2 and 1 equiv of PPh3 in CH2Cl2. X-ray analysis shows 5 adopts a distorted-square-planar structure consisting of PPh3, X, and PhCH=CH-(PPh3)+ as ligands. The PPh3 ligand is trans to the olefin carbon that is connected to the PPh3 group in PhCH=CH(PPh3)+, while the halide ligand is trans to the olefin carbon bonded to a phenyl moiety. Reaction of 5 (X = Br) with 1 equiv of PPh3 at ambient temperature afforded 1 in high yield. Pd(PPh3)4 or Pd(OAc)2 catalyzes the reactions of PPh3 with PhCH=CHBr, MeCH=CHBr, MeCH=C(Me)Br (mixtures of isomers), CH2=C(Me)Br, cis-(EtO2C)CH=CHBr, and cis-(MeO2C)CH=CHBr to give the corresponding trans-RCH=CR?(PPh3)+Br-. During the reaction of PPh3 with PhCH=CHBr, 1 was found to be a catalyst intermediate in the reaction solution. All the phosphonioalkene-palladium(0) complexes and alkenylphosphonium halides isolated are trans in the (RCH=CR?PPh3)+ moiety.

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

Some scientific research about Tetrakis(acetonitrile)palladium(II) tetrafluoroborate

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Synthesis and characterization of palladium(II)-phosphole and – biphosphole complexes. Regulation of the homoleptic coordination environment of square-planar palladium(II)

A series of novel square-planar palladium(II)-phosphole complexes was synthesized in good yields by a ligand-substitution reaction of [Pd(CH3CN)4](BF4)2 with 3,4-dimethyl-1-phenylphosphole (dmpp) and/or 3,3’4,4′-tetramethyl1,1′-diphenyl-2,2′-biphosphole (bidmpp) in CH2Cl2; [Pd(dmpp)4](BF4)2 (1), [Pd(bidmpp)(dmpp)2](BF4)2 (2), and [Pd- (bidmpp)2](BF4)2 (3). Those complexes were characterized by 1H and 31 PNMR spectroscopies and X-ray crystallography for 3. The crystal structure of 3 revealed that the configurations of the phosphorus atoms were (R, R, S, S), indicating that the structure was a meso form with an intramolecular pi-pi interaction between the phenyl groups. 1HNMR spectroscopy suggested the structures of 1 and 2: Complex 1 has a water wheel-like C(4h) structure and complex 2 is C2 symmetric. In the 31PNMR spectra of those complexes, each resonance showed a smaller downfield shift than that observed for [Pd(dppe)2]Cl2 (dppe = 1,2-bis(diphenylphosphino)ethane), indicating that the palladium-phosphole interaction is governed by mainly a sigma-donation, and that there is a small contribution from a pi-back bonding interaction.

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

More research is needed about Pd2(DBA)3

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Triplet photosensitizer-nanotube conjugates: Synthesis, characterization and photochemistry of charge stabilizing, palladium porphyrin/carbon nanotube conjugates

The ability of a triplet photosensitizer to generate long-lived charge separated states, in contrast to traditionally used singlet photosensitizers, in covalently functionalized single-walled carbon nanotube hybrids has been investigated. Enriched single-walled carbon nanotubes with two diameters, namely (6,5) and (7,6), were covalently modified to carry a charge-stabilizing triplet photosensitizer derived from a palladium porphyrin. The nanohybrids were fully characterized and the presence of intramolecular interactions between the porphyrin and nanotubes was established from various spectroscopic, imaging, electrochemical and thermochemical studies. Photoluminescence of palladium porphyrin was found to be quantitatively quenched in the presence of covalently appended SWCNTs and this quenching is due to excited state charge separation and has been established by femtosecond transient absorption studies. Owing to the presence of the triplet photosensitizer, the charge separated states lasted over 3 ns, i.e., much longer than those reported earlier for singlet photosensitizer-derived nanotube hybrids. The nanohybrids also exhibited efficient photocatalytic behavior in experiments involving electron pooling of one-electron reduced methyl viologen in the presence of a sacrificial electron donor. Higher yields of photoproducts were achieved from the present donor-acceptor nanohybrids when compared with those of singlet photosensitizer-derived nanohybrids, more so for (6,5) nanotube derived hybrids compared to (7,6) nanotube derived hybrids. The present findings highlight the importance of triplet photosensitizer derived nanohybrids in artificial photosynthesis of charge separation and photocatalytic applicatons.

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

Awesome Chemistry Experiments For 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex

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Synthesis, structural characterization, and catalytic evaluation of palladium complexes with homologous ferrocene-based pyridylphosphine ligands

A ferrocene-based phosphinopyridine, Ph2PfcPy (1; fc = ferrocene-1,1′-diyl, Py = 2-pyridyl), was newly synthesized by Negishi coupling of Ph2PfcZnCl with PyBr. Its homologous compound Ph2PfcCH 2Py (2) was obtained by reductive dehydroxylation of Ph 2PfcCH(OH)Py (4), the latter resulting via reaction of in situ generated Ph2PfcLi with PyCHO. Depending on the stoichiometry, compounds 1 and 2 react with [PdCl2(cod)] (cod = eta2:eta2- cycloocta-1,5-diene) to give P,N-chelate and bis-phosphine complexes, [PdCl 2(L-?2P,N)] (5, L = 1;6, L = 2) and [PdCl 2(L-?P)2] (7, L = 1;8, L = 2), respectively. Analogously, [(LNC)PdCl]2 or [(LNC)Pd(MeCN) 2]ClO4 (LNC = [(2-dimethylamino-?N)methyl] phenyl-?C1) react with 1 and 2 to afford complexes featuring these compounds as P-monodentate ligands ([(LNC)PdCl(L-?P)]: 9, L = 1;10, L = 2) or P,N-chelating donors ([(LNC)Pd(L-?2P,N)]ClO 4: 11, L = 1;12, L = 2), respectively. With the exception of compound 9, which undergoes self-ionization in solution, all complexes are defined air-stable solids and were characterized by elemental analysis and conventional spectroscopic methods (multinuclear NMR, IR, and MS). The crystal structures of 4, 5, 7 3 CH2Cl2, 8, 11, and 12 were determined by X-ray crystallography, revealing structural differences resulting from a more flexible geometry of the methylene-spaced ligand 2. The catalytic potential of the Pd complexes 5 and 6 and their in situ generated counterparts (Pd(OAc) 2/L, L = 1, 2) was studied in Suzuki-Miyaura cross-coupling of 4-bromotoluene (13) with phenylboronic acid and in cyanation of the same substrate with K4[Fe-(CN)6]. The results were compared with those obtained under identical conditions with analogous catalysts based on the related donor-symmetric ligand 1,1′-bis(diphenylphosphino)ferrocene.

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