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

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Palladium(II) complexes with 1,1?-bis(diphenylphosphino)ferrocenes [Fe(eta5-C5R4PPh2)2] n+ (dppf, R = H, n = 0; dppomf, R = Me, n = 0; dppomf+, R = Me, n = 1). Synthesis, characterization, and catalytic activity in ethene methoxycarbonylation

Several palladium(II) complexes with 1,1?-bis(diphenylphosphino)octamethylferrocene (dppomf) and its oxidized form 1,1?-bis(diphenylphosphino)octamethylferrocenium (dppomf) have been synthesized and characterized by spectroscopic and electrochemical methods. For comparative purposes, analogous Pd(II) derivatives with 1,1?-bis(diphenylphosphino)ferrocene (dppf) have been also prepared. Single-crystal X-ray analyses have been carried out for the square-planar mononuclear compounds [Pd(H2O)2(dppf)](OTf)2 and [Pd(H2O)2(dppomf)](OTf)2 and for the binuclear complex [Pd(mu-OPF2O)(dppomf+)]2(BF4) 4¡¤6CH2Cl2 in which two [Pd(dppomf+)]3+ moieties are held together by the oxygen atoms of two bridging PO2F2 groups derived from the oxidative degradation of PF6 ions. Selected dppf and dppomf Pd(II) complexes have been employed as catalyst precursors for the methoxycarbonylation of ethene (600 psi, 1:1 CO/C2H4, 85 C). It has been found that dppomf generates selective catalysts for the production of methyl propanoate, while dppf leads to a variety of low-molecular-weight oxygenates spanning from methyl propanoate to alternating oligoketones.

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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 new heterobimetallic palladium-[60]fullerene complex with bidentate bis-1,1?-[P]2-ferrocene ligand

A new heterobimetallic palladium-[60]fullerene complex with ferrocene bis-phosphine ligand was prepared using alternative paths: either via addition reaction of Pd2(dba)3¡¤C6H6 (dba=dibenzylidenacetone) in the presence of 1,1?-bis(diphenylphosphino)ferrocene (dppf) to C60, or via electrochemical activation of C60 to generate C602- anions, which then react with PdCl2 and dppf to yield the target complex. The obtained (eta2-C60)Pd(dppf) complex was characterized by 1H- and 31P-{1H}-NMR and electronic spectroscopy as well as electrochemically.

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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, structures, and optical and electrochemical characteristics of novel crown-containing polythiophene systems

The synthesis, structures, and optical and electrochemical characteristics of novel crown-containing styryl mono-and polythiophenes were described. The double bonds were constructed by the Horner-Wadsworth-Emmons method. The Suzuki and Stille cross-coupling reactions were used to create polythiophene chains. Optical measurements revealed intense absorption and fluorescence of crown-containing polythiophenes; the band positions and shapes in their absorption and emission spectra depend on the structure of the polythiophene. The electrochemical characteristics of the compounds obtained were measured.

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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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Palladium-Catalyzed Three-Component Reaction: A Novel Method for the Synthesis of N-Acyl Propiolamides

Palladium-catalyzed three-component reactions between terminal alkynes, isonitriles, and sodium carboxylates have been developed. This novel and operationally simple methodology provides an alternative for the synthesis of N-acyl propiolamide derivatives under mild conditions using isonitriles as the amine source and sodium carboxylates as the oxygen and acyl source.

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

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Synthetic and structural studies on linear and macrocyclic Pd- and Pt-bridged butterfly Fe/S cluster complexes

Three types of (diphosphine)Pd- or Pt-bridged butterfly Fe/S cluster complexes have been prepared by a simple and convenient one-pot synthetic method. The first type of such complexes involves the linear (diphosphine)Pd- or Pt-bridged double-butterfly Fe/S clusters [(mu-RS)(mu-S=CS)Fe2(CO)6]2[M-(diphosphine)] (1-12; M = Pd and Pt; R = Et, t-Bu, Ph, and p-MeC6H4; diphosphine = dppe, dppv, and dppf), which were prepared by sequential reactions of monoanions [(mu-RS)(mu-CO)-Fe2(CO)6]- (formed in situ from Fe3(CO)12, RSH, and Et3N) with excess CS2, followed by treatment of the resulting monoanions [(mu-RS)(mu-S=CS)Fe2(CO)6]- with (diphosphine)MCl2. The second type of complexes involves the macrocyclic (diphosphine)M-bridged double-butterfly Fe/S clusters [mu-S(CH2)4S-mu][(mu-S=CS)-Fe2(CO)6]2[M(diphosphine)] (13-16; M = Pd and Pt; diphosphine = dppe and dppv), which were prepared by sequential reactions of dianion [{mu-S(CH2)4S-mu}{(mu-CO)Fe2(CO)6}2]2- (generated in situ from Fe3(CO)12, dithiol HS(CH2)4SH, and Et3N) with excess CS2, followed by treatment of the resultant dianion [{mu-S(CH2)4S-mu}{(mu-S=CS)Fe2(CO)6}2]2- with (diphosphine)MCl2. In contrast, when dithiol HS(CH2)4SH was replaced by HS(CH2)3SH (a dithiol with a shorter carbon chain), the aforementioned sequential reactions afforded the third type of macrocyclic complexes which involves the (diphosphine)M-bridged quadruple-butterfly Fe/S clusters [{mu-S(CH2)3S-mu}{(mu-S=CS)Fe2(CO)6}2]2[M(diphosphine)]2 (17-20; M = Pd and Pt; diphosphine = dppe and dppv). While the two possible pathways are suggested for production of the two types of novel macrocyclic Fe/S clusters 13-20, respectively, all new complexes 1-20 have been characterized by elemental analysis, spectroscopy, and, for some of them particularly, DFT calculations and X-ray crystallography.

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

Final Thoughts on Chemistry for 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex

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COMPOUND HAVING BRANCHED ALKYL OR BRANCHED ALKENYL, OPTICALLY ISOTROPIC LIQUID CRYSTAL MEDIUM AND OPTICAL ELEMENT

The first object of the invention is to provide a liquid crystal compound that is stable to heat, light and so on, and has a large optical anisotropy, a large dielectric anisotropy and a low melting point. The second object is to provide a liquid crystal medium that is stable to heat, light and so on, has a broad temperature range of a liquid crystal phase, a large optical anisotropy and a large dielectric anisotropy, and exhibits an optically isotropic liquid crystal phase. The third object is to provide a variety of optical elements containing the liquid crystal medium, which can be used in a broad temperature range and has a short response time, a high contrast and a low driving voltage. A liquid crystal compound with branched alkyl or branched alkenyl as represented by formula (1), a liquid crystal medium (a liquid crystal composition or a polymer/liquid crystal composite material) containing the liquid crystal compound, and an optical element containing the liquid crystal medium are described. In formula (1), R1 is branched alkyl of C3-20 or branched alkenyl of C3-20. The ring A1, A2, A3, A4 or A5 is 1,4-phenylene or 1,3-dioxane-2,5-diyl, for example. Z1, Z2, Z3 and Z4 are independently a single bond or C1-4 alkylene, for example. Y1 is fluorine, for example, m, n and p are independently 0 or 1, and 1?m+n+p?3.

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

A new application about 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex

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Palladium catalyzed desulfinylative couplings between aryl sulfinates and aryl bromide/iodide for the synthesis of biaryls

We have synthesized biaryls from the coupling reaction between aryl sulfinates and aryl halides using homogeneous palladium catalytic system. The developed method is simple and efficient. These methodologies are particularly useful to prepare symmetrical as well as unsymmetrical biaryls with excellent product yield. The suggested protocol demonstrated a broad substrate scope.

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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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Synthesis of polyarylated methanes through cross-coupling of tricarbonylchromium-activated benzyllithiums

Support group: Coordinated to the tricarbonylchromium fragment, a typically unstable benzylic organolithium can participate directly in cross-coupling reactions with aryl bromides to form polyarylated methane derivatives (see scheme). Cr(CO)3 assistance leads to reactivity with a variety of coordinated substrates and-given multiple benzylic sites-can effect up to six coupling events per arene. “Chemical equation presented”

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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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Palladium-catalyzed cross-coupling reactions of dithienosilole with indium reagents: Synthesis and characterization of dithienosilole derivatives and their application to organic light-emitting diodes

Three dithienosilole (DTS) derivatives bearing naphthyl segments, 5,5?-dinaphthyl-1,1-dimethyldithienosilol (1), 5,5?-dinaphthyl-1- methyl-1-phenyldithienosilole (2), and 5,5?-dinaphthyl-1,1- diphenyldithienosilol (3), are prepared through Pd(II)-catalyzed cross-coupling using an organoindium reagent as a nucleophile. The molecular structure of 3 is confirmed by single-crystal X-ray analysis. In addition, thermal, photophysical, and electrochemical properties for all three compounds are systematically investigated. The introduction of naphthyl segments into the DTS framework leads to an excellent enhancement of thermal stability with relatively high glass transition (Tg: 87 C) and decomposition temperatures (T d: 320-380 C). A red shift in both absorption and emission is observed in the DTS series as the 1,1-substituents on the ring silicon atom become more electronegative. On the basis of absorption spectra and DFT/TDDFT calculations, intense green photoluminescence observed for all compounds can be attributed to the effective pi-pi* transition of the DTS and naphthyl group with a small contribution of the sigma* orbital of the exocyclic Si-C bond. The electron-transporting properties of 1, 2, and 3 were evaluated by the performance of organic light-emitting diodes (OLEDs), comprising 4,4?,4??-tris(N-(2-naphthyl)-N-phenylamino)triphenylamine (2-TNATA) as hole-injection layer, 4,4?-bis(N-phenyl-1-naphthylamino) biphenyl (NPB) as hole-transport layer, 10-(2-benzothiazolyl)-1,1,7,7- tetramethyl-2,3,6,7-tetrahydro-1H,5H,11H-benzo[l]pyrano[678-ij] quinolizin-11-one(C545T)/tris(8-quinolinato)aluminum (Alq3) as emitting layer, and the DTS series as electron-transporting layer, respectively. The device shows intense green emission with a high efficiency of 8.0 cd/A at 1000 cd/m2.

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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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Pd-catalyzed intramolecular Heck reaction for the synthesis of 2-methylbenzofurans

A new strategy for the synthesis of 2-Methylbenzofurans via the intramolecular Heck reaction has been developed. This efficient palladium-catalyzed system showed good catalytic activity. Various substituted 2-methylbenzofurans could be afforded in good to excellent yields.

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