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A new procedure was developed for the synthesis of a broad range of ansa-zirconocenes containing bis(2-methyl-4-arylindenyl)dimethylsilane ligands. The method is based on the palladium-catalyzed reaction of halogen-substituted bis(indenyl)dimethylsilanes with various organozinc compounds. The aryl-substituted bridging ligands thus prepared serve as the starting compounds for the synthesis of ansa-zirconocenes, which can be used as components of promising catalysts for propylene polymerization.

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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 donor-acceptor red fluorescent dye bis(4-(N-(9,9-diethyl-2-fluorenyl)-3, 5-dimethyl-phenylamino)phenyl)fumaronitrile (FMPAFN), and a blue fluorescent dye 2,7-bis(N-2-(9,9-diethylfluorenyl)-3,5-dimethylphenylamino)-9,9-diethylfluorene (FMPAEF), were synthesized, characterized, and used as active materials in non-doped electroluminescent devices. Emission peaks from three-layered or four-layered devices using FMPAFN dye centered at 680 or 684 nm with their Commision Internationale de I’Eclairage (CIE) color coordinates of (0.671, 0.310) or (0.673, 0.309). Current efficiencies of 1.89 or 3.55 cd/A for the FMPAFN devices were achieved, respectively. Similar non-doped three-layered or four-layered devices based on blue FMPAEF dye emitted at 424 or 456 nm with full widths at half maximum of 63 and 101 nm and CIE (x,y) of (0.181, 0.138) or (0.185, 0.189), respectively. Current efficiencies of the FMPAEF devices were 0.57 or 1.04 cd/A. In these devices, both dyes are multifunctional, acting as emitters as well as hole-transporting materials. The emission colors were tuned by both the non-planar arylamino group and the centric core (fumaronitrile or fluorene bridge), revealing potential applications in electroluminescent devices.

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

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New neutral and cationic complexes [NiBr2(L1)] (1), [NiBr 2(OPHPh2)(L1)] (2), [NiMe2(L1)] (3), [NiBr(PMe3)(L1)](Br) (4), [Ni(CH3CN)(PMe 3)(L1)](BF4)2 (5), [PdBr2(L1)] (6), [PdI2(L1)] (7), [PtMeCl(L1)] (8), [PtMe2(L1)] (9), [Pt(CH3CN)2(L1)](BF4)2 (10), [Pt(L1)2](X)2 [X = Cl (11a), Br (11b)], [PtX(L1) 2](X) [X = Cl (12a), Br (12b)], where L1: [Ph2PCH 2C(Ph)=N(2,6-Me2C6H3)2] and L2: [Ph2PCH2C(Ph)= N(2,6-iPr 2C6H3)2], have been prepared and characterised. The molecular structures of 1, 2, 6, 7 and 9 have been determined. The complexes [PdBr2(L2)] (6), [PdBr2(L1)] and [PdMeCl(L1)] have been found to catalyse the Heck coupling of 4-bromoacetophenone with n-butyl acrylate under aerobic conditions. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2005.

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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 decarboxylative allylation of arylglyoxylic acids with allyl alcohol has been developed. In the presence of catalytic amounts of Pd(dba) 2 and PPh3, the substrates are in an esterification equilibrium with the allyl arylglyoxylates, which are continuously decarboxylated to give alpha,beta-unsaturated ketones along with CO2 and water as the only byproducts.

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

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We report the total syntheses of (-)-indolactam V and the C7-substituted indolactam alkaloids (-)-pendolmycin, (-)-lyngbyatoxin A, and (-)-teleocidin A-2. The strategy for preparing indolactam V relies on a distortion-controlled indolyne functionalization reaction to establish the C4-N linkage, in addition to an intramolecular conjugate addition to build the conformationally-flexible nine-membered ring. The total synthesis of indolactam V then sets the stage for the divergent synthesis of the other targeted alkaloids. Specifically, late-stage sp2-sp3 cross-couplings on an indolactam V derivative are used to introduce the key C7 substituents and the necessary quaternary carbons. These challenging couplings, in addition to other delicate manipulations, all proceed in the presence of a basic tertiary amine, an unprotected secondary amide, and an unprotected indole. Thus, our approach not only enables the enantiospecific total syntheses of four indolactam alkaloids, but also serves as a platform for probing complexity-generating and chemoselective transformations in the context of alkaloid total synthesis. This journal is the Partner Organisations 2014.

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

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Mixtures of Pd(dba)2 + 2L-L (where L-L is a bidentate ligand such as dppm, dppe, dppp, dppb, dppf, and DIOP) lead to the formation of Pd(L-L)2 complexes which do not undergo an oxidative addition with phenyl iodide. Mixtures of Pd(dba)2 + 2 BINAP do not afford Pd(BINAP)2 but Pd(dba)(BINAP). Mixtures of Pd(dba)2 + IL-L (L-L = dppm, dppe, dppp, dppb, dppf, DIOP, and BINAP) lead to Pd(dba)(L-L) complexes via the formation, at short time, of the complex Pd(L-L)2, except for dppf and BINAP where the complex Pd(dba)(L- L) is directly formed. Pd(dba)(L-L) is the main complex in solution but is involved in an endergonic equilibrium with the less ligated complex Pd(L-L) and dba. Pd(L-L) is the more reactive species in the oxidative addition with phenyl iodide. However, Pd(dba)(L-L) also reacts in parallel with phenyl iodide. From the kinetic data concerning the reactivity of these different catalytic systems in the oxidative addition with phenyl iodide, one observes the following order of reactivity: Pd(dba)2 + 1DIOP > Pd(dba)2 + 1dppf >> Pd(dba)2 + 1BINAP. All these systems associated to one bidentate ligand are less reactive than Pd(dba)2 + 2PPh3.

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

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N-Arylamido complexes of zirconium in which the amido functional group is attached to an o-(alkyliminoethyl) substituted aromatic ring, have been synthesised by salt elimination reactions and characterised by spectroscopic and diffraction methods; they are analogous to the N-silylamido species recently reported (Dalton Trans., 2002, 3290-3299). The ligands 2-[CyN=C(CH 3)]C6H4N(H)(xyl), LxylH, and 2-[CyN=C(CH3)]C6H4N(H)(mes) LmesH, Cy – C6H11, xyl = 3,5-Me2C6H 3 mes = 2,4,6-Me3C6H2, were prepared in good yields by Buchwald-Hartwig amination of the arylbromides with 2-[CyN=C(CH3)]C6H4NH2. Reaction of LmesLi with Zr(NEt2)2Cl2(thf) 2 gave after chloride substitution the arylamido ketimino complex LmesZr(NEt2)2Cl 1; variable amounts of the arylamido vinylamido complex 2 were also obtained. Interaction of L mesLi or LxylLi with Ti(NMe2) 2Cl2 gave rise to the tripodal bis-amido amino complexes 5 and 6 possibly formed by ligand rearrangement involving migration of the dimethylamido group to the ketimino carbon.

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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 catalytic synthesis of isobutanol (iBuOH), via the Guerbet condensation of methanol with n-propanol is described. In particular, bifunctional catalysts based on either heterogeneous or homogeneous dehydrogenating/hydrogenating palladium species and on sodium methoxide (MeONa) as basic component were investigated. When heterogeneous Pd/C and MeONa was used as catalytic system a high activity was obtained with turnover numbers up to about 110mol of iBuOH/(mol of Pd h). The increase of the MeONa/Pd molar ratio increased the activity of the catalyst. However, differently from Cu-based/MeONa catalysts, a significant metal leaching was observed; recycle experiments indicated that both heterogeneous and homogeneous palladium species are involved in the catalysis. When homogeneous palladium complexes, such as tetrakis(triphenylphosphine)palladium(0) [Pd(PPh3)4] diphenylphosphinoethane(dichloro)palladium(II) [Pd(dppe)Cl2] and bis(dibenzylideneacetone)palladium(0) [Pd(dba)2], were used in combination with MeONa a remarkable activity was also obtained, independently of the oxidation state of the palladium precursor. During the reaction deposition of a solid was observed and recycle experiments carried out both on the recovered solid and on the liquid phase suggested that also in this case the activity has to be addressed to both heterogeneous and homogeneous (or colloidal) palladium species.

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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 two-step (nucleophilic substitution/palladation by oxidative addition) sequence provides a high-yielding access to a non-symmetrical palladium NNC pincer complex. A number of terminal and internal alkynoic acids with different substitution patterns at the alpha- and beta-positions are regio- and diastereoselectively cycloisomerized to the corresponding exocyclic enol lactones in the presence of exceedingly low amounts of the latter palladium complex, so that unprecedented turnover numbers and frequencies ranging from 1,000,000 to 700,000 and from 41,667 to 9722 h?1, respectively, are achieved. The optimized protocol, based on the use of a catalytic amount of triethylamine as base, allows an easy real-time monitoring of the reaction by NMR spectroscopy. Several pieces of evidence in favor of the direct participation of the above pincer complex as the catalyst of the reaction have been gathered from kinetic and poisoning experiments. (Figure 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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Herein, we report a Pd-catalysed alkoxycarbonylation of alkenes based on the use of a recyclable CO2 reduction product, the crystalline and air-stable N-formylsaccharin, as a CO surrogate. The carbonylation proceeds under ambient conditions in an exceptionally complementary regioselective fashion yielding the desired branched products from styrene derivatives and valuable linear esters from alkyl-substituted alkenes.

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