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Synthesis of novel conjugated polymers based on benzo[1,2-: D:4,5- d ?]-bis([1,2,3]triazole) for applications in organic field-effect transistors

Novel donor-acceptor (D-A) conjugated polymers based on 4,8-bis(5-bromothiophen-2-yl)-2,6-bis(2-octyldodecyl)-2H-benzo[1,2-d:4,5-d?]- bis([1,2,3]triazole)-6-ium-5-ide (BTBBTa) combined with three different electron-donating monomers bithiophene (BT), thieno[3,2-b]thiophene (TT), (E)-2-[2-(thiophen-2yl)vinyl]thiophene (TVT) were synthesized. By replacing the sulfur atoms on benzobisthiadiazole with nitrogen atoms, benzobistriazole (BBTa) can possess alkyl chains on the central nitrogen atoms rather than on the thiophene rings along the polymer chain, which can reduce the steric hindrance between neighboring monomers and increase the planarity of polymers. The optical, thermal and electrochemical properties of the polymers were characterized, respectively. DFT calculations were used to calculate the optimized geometries of polymer backbones. The thin film microstructures of the polymers were characterized by using GIWAXS and AFM. In these novel polymers, PBTBBTa-BT displayed the highest hole mobility of 0.21 cm2 V-1 s-1.

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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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Synthesis of C2-symmetric benzimidazolium salts and their application in palladium-catalyzed enantioselective intramolecular alpha-arylation of amides

A series of C2-symmetric chiral benzimidazolium salts, the precursor of N-heterocyclic carbene ligands, were designed and synthesized from 1,2-dibromobenzene. In situ prepared corresponding carbenes were tested in the asymmetric palladium-catalyzed intramolecular alpha-arylation of amides, affording chiral diarylmethanols with high yields and moderate enantioselectivities.

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

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Anti-Carboalumination of Alkynes Using Aluminum Trihalide and Silyl Ketene Imines: Stereo- and Regioselective Synthesis of Alkenylaluminum Compounds Bearing a Cyano Group

An organoaluminum-free and catalyst-free anti-carboalumination of alkynes using aluminum trihalides and silyl ketene imines was developed. Three components, an alkyne, AlX3, and a silyl ketene imine, were simply mixed to give the alkenylaluminum bearing a cyano group with regioselectivity. Theoretical calculations revealed the effective activation of the alkyne by AlX3 to enhance the regioselective carboalumination. The synthesized alkenylaluminums were applicable to many organic transformations.

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

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Selective synthesis of multisubstituted olefins utilizing gem – And vic -diborylated vinylsilanes prepared by silylborylation of an alkynylboronate and diborylation of alkynylsilanes

The synthesis of a series of gem- and vic-diborylated vinylsilanes was accomplished via highly selective transition-metal-catalyzed syn-dimetalation to the alkynylmetal species. This protocol served as a general synthetic method toward regio- and stereodefined multisubstituted olefins. The key steps are the diastereoselective Suzuki-Miyaura cross-coupling reactions of gem- and vic-diborylated vinylsilanes, in which the two boron groups showed discrete reactivities to afford diverse precursors of multisubstituted olefins.

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

Can You Really Do Chemisty Experiments About 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex

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Late-stage functionalization of 1,2-dihydro-1,2-azaborines via regioselective iridium-catalyzed C-H borylation: The development of a new N,N-bidentate ligand scaffold

The first general late-stage functionalization of monocyclic 1,2-azaborines at the C(6) position is described. Ir-catalyzed C-H borylation occurs regioselectively at the C(6) position of B-substituted 1,2-azaborines and is compatible with a range of substitution patterns at boron (e.g., hydride, alkoxide, alkyl, and aryl substituents). Subsequent Suzuki cross coupling with aryl- and heteroaryl bromides furnishes 1,2-azaborine-based biaryl compounds including 6-[pyrid-2-yl]-1,2-azaborines that represent novel kappa2-N,N-bidentate ligands. The 6-[pyrid-2-yl]-B-Me-1,2-azaborine ligand has been demonstrated to form an emissive coordination complex with dimesitylboron that exhibits bathochromically shifted absorption and emission maxima and a higher photoluminescence quantum yield compared to its carbonaceous analogue.

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

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Palladium-Catalyzed Carbonylation of Aryl Chlorides to Electrophilic Aroyl-DMAP Salts

The palladium-catalyzed carbonylative coupling of aryl chlorides and 4-dimethylaminopyridine (DMAP) to generate electrophilic aroyl-DMAP salts is described. In contrast to classical carbonylation reactions, which often require nucleophiles to react with weakly electrophilic palladium-acyl intermediates, the high electrophilicity of aroyl-DMAP salts allows the acylation of a broad range of substrates. This transformation is mediated by a palladium-Xantphos catalyst, and mechanistic studies suggest the combination of ligand steric strain together with Pd(0) stabilization allows both the reductive elimination of a reactive ArCO-DMAP product and oxidative addition of the strong aryl-chloride bond. Overall, this transformation allows the generation of amides and esters from aryl chlorides with an array of nucleophiles and with good functional group compatibility.

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

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A tandem and tunable Pd catalyzed C-N coupling of heteroarenols with ureas via C-OH bond activation

At this circumstance for the first time, a facile and convenient method for heteroaryl ureas has been developed via a two-step process involving in situ C-OH activation followed by palladium catalyzed C-N coupling of heteroarenols with ureas, which show excellent functional group tolerance and give out rapid coupling in good to excellent yield.

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

Brief introduction of Bis(tri-tert-butylphosphine)palladium

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Homoleptic tetrakis(silyl) complexes of Pd0 and Pt0 featuring metal-centred heterocubane structures: Evidence for the existence of the corresponding mononuclear PdI and PtI complexes

We report on the first homoleptic tetrakis(silyl) complexes of zerovalent Group 10 metals. The compounds [MLi4{Si(3,5-Me2pz) 3}4] (M=Pd and Pt; 3,5-Me2pz=3,5- dimethylpyrazolyl) exhibit very appealing metal-centred heterocubane structures with the central d10 metal atoms surrounded by four silicon and four lithium atoms. Both compounds were characterised in detail, including X-ray crystal-structure analysis and 2D NMR spectroscopic methods such as 7Li,29Si and 7Li,195Pt HMQC. Cyclic voltammetry studies, in combination with density functional theory (DFT) calculations, revealed that the corresponding mononuclear cationic d 9-MI and dicationic d8-MII complexes are accessible by stepwise one-electron oxidation of the title compounds. Electron paramagnetic resonance (EPR) investigations provided evidence for the existence of the corresponding paramagnetic palladium(I) and platinum(I) complexes. Unusual oxidation states: Tetrakis(silyl) complexes of the zerovalent Group 10 metals, palladium and platinum, featuring metal-centred heterocubane structures have been synthesised and characterised in detail (see picture). Electron paramagnetic resonance (EPR) investigations provided evidence for the existence of the corresponding paramagnetic palladium(I) and platinum(I) complexes. Copyright

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

New explortion of Tris(dibenzylideneacetone)dipalladium-chloroform

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Single-step assembly of a C2-symmetrical palladium(IV) spirocyclic complex

A pair of seven-membered chelate rings are found in the palladium(IV) complex assembled in only a single step from commercially available [Pd2(dba)3], tetrachloro-1,2-benzoquinone, and norbornene. The structure consists of a C2-symmetrical palladaspirocycle framework and an ether ligand, as confirmed by X-ray analysis of the thf complex (see picture).

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

Archives for Chemistry Experiments of Pd2(DBA)3

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4-[18f]fluorophenylpiperazines by improved hartwig-buchwald n-arylation of 4-[18f]fluoroiodobenzene, formed via hypervalent lambda3-Iodane precursors: Application to build-up of the dopamine d4 ligand [18f]fauc 316

Substituted phenylpiperazines are often neuropharmacologically active compounds and in many cases are essential pharmacophores of neuroligands for different receptors such as D2 -like dopaminergic, serotoninergic and other receptors. Nucleophilic, no-carrier-added (n.c.a.) 18F-labelling of these ligands in an aromatic position is desirable for studying receptors with in vivo molecular imaging. 1-(4-[18 F]Fluorophenyl)piperazine was synthesized in two reaction steps starting by 18F-labelling of a iodobenzene-iodonium precursor, followed by Pd-catalyzed N-arylation of the intermediate 4-[18F]fluoro-iodobenzene. Different palladium catalysts and solvents were tested with particular attention to the polar solvents dimethylformamide (DMF) and dimethylsulfoxide (DMSO). Weak inorganic bases like potassium phosphate or cesium carbonate seem to be essential for the arylation step and lead to conversation rates above 70% in DMF which is comparable to those in typically used toluene. In DMSO even quantitative conversation was observed. Overall radiochemical yields of up to 40% and 60% in DMF and DMSO, respectively, were reached depending on the labelling yield of the first step. The fluorophenylpiperazine obtained was coupled in a third reaction step with 2-formyl-1H-indole-5-carbonitrile to yield the highly selective dopamine D4 ligand [18F]FAUC 316.

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