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Titanocenes of the formula I STR1 in which R1 are cyclopentadienyl? groups and R2 and R3 are aromatic radicals which are substituted in both ortho-positions by fluorine and, in addition, are substituted by a pyrrylalkyl group, amidoalkyl group or imidoalkyl group, are suitable as photoinitiators for the photopolymerization of ethylenically unsaturated compounds.

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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 palladium-catalyzed multicomponent synthetic route to polysubstituted pyrroles from aryl iodides, imines, carbon monoxide, and alkynes is described. To develop this reaction, a series of mechanistic studies on the [Pd(allyl)Cl]2/PtBu3 catalyzed synthesis of imidazolinium carboxylates from aryl iodides, imines, and carbon monoxide were first performed, including model reactions for each individual step in the transformation. These show that this reaction proceeds in a concurrent tandem catalytic fashion, and involves the in situ formation of acid chlorides, N-Acyl iminium salts, and ultimately 1,3-dipoles, i.e., Muenchnones, for subsequent cycloaddition. By employing a Pd(PtBu3)2/Bu4NCl catalyst, this information was used to design the first four-component synthesis of Muenchnones. Coupling the latter with 1,3-dipolar cycloaddition with electron deficient alkynes or alkenes can be used to generate diverse families of highly substituted pyrroles in good yield. This represents a modular and streamlined new approach to this class of heterocycles from readily accessible starting materials.

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

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Reductive elimination from Pd(II) aryl trifluoromethyl complexes is a challenging and elusive step which is accompanied by a number of kinetically more favorable side reactions giving rising to a complex mixture. We report herein the synthesis and isolation of several arylPd(II) trifluoromethyl complexes (2a-c) and study their electronic structures, photophysical properties and reductive elimination reactivities. A remarkable concentration effect on chemoselectivity is observed for thermal decomposition of (Xantphos)Pd(II)(Ar)(CF3) (2c) that favors the formation of Ar-CF3 at lower concentrations, but gives increasingly more Ar-Ar homocoupling product to a dominant extent as the concentration of 2c increases. This is solid evidence for the involvement of an intermolecular Ar/CF3 ligand exchange/Ar-Ar reductive elimination mechanism that has been proposed based on DFT computational studies. The interplay between theory and experiment provides valuable insights into the mechanism and kinetics of the key elementary reaction of reductive elimination at Pd(II), and may thus prompt the design of more efficient Pd-mediated nucleophilic trifluoromethylation reactions.

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

Discovery of Bis(tri-tert-butylphosphine)palladium

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The alkali-metal salts (potassium and sodium) of a large number of aryl- and heteroarylsilanols undergo efficient cross-coupling with a wide range of aromatic bromides and chlorides under mild conditions to form polysubstituted biaryls. The critical feature for the success of these coupling reactions and their considerable scope is the use of bis(tri-tert-butylphosphine)palladium. Under the optimized conditions, electron-rich, electron-poor, and sterically hindered arylsilanolates afford cross-coupling products in good yields. Many functional groups are compatible with the coupling conditions such as esters, ketones, acetals, ethers, silyl ethers, and dimethylamino groups. Two particularly challenging substrates, (2-benzofuranyl)dimethylsilanolate and (2,6-dichlorophenyl)dimethylsilanolate prepared as their sodium salts showed excellent activity in the coupling reactions, in the former case also with aromatic chlorides. General methods for the efficient synthesis of a wide range of aromatic silanols are also described.

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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 title reaction of silylethynyl 2,6-(tBu)2phenyl ethers took place in the presence of a palladium catalyst and pivalic acid to give 2-silylmethylenechromanes. The initial products were converted by treatment with aceticacid to thermodynamically stable 4H-chromenes, which were further reacted with activated aldehyde and ketone.

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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 series of monomeric arylpalladium(II) complexes LPd(Ph)X (L = 1-AdP tBu2, PtBu3, or Ph 5FcPtBu2 (Q-phos); X = Br, I, OTf) containing a single phosphine ligand have been prepared. Oxidative addition of aryl bromide or aryl iodide to bis-ligated palladium(0) complexes of bulky, trialkylphosphines or to Pd(dba)2 (dba = dibenzylidene acetone) in the presence of 1 equiv of phosphine produced the corresponding arylpalladium(II) complexes in good yields. In contrast, oxidative addition of phenyl chloride to the bis-ligated palladium(0) complexes did not produce arylpalladium(II) complexes. The oxidative addition of phenyl triflate to PdL2 (L = 1-AdPtBu2, PtBu 3, or Q-phos) also did not form arylpalladium(II) complexes. The reaction of silver triflate with (1-AdPtBu2)Pd(Ph)Br furnished the corresponding arylpalladium(II) triflate in good yield. The oxidative addition of phenyl bromide and iodide to Pd(Q-phos)2 was faster than oxidative addition to Pd(1-AdPtBu2)2 or Pd(PtBu3)2. Several of the arylpalladium complexes were characterized by X-ray diffraction. All of the arylpalladium(II) complexes are T-shaped monomers. The phenyl ligand, which has the largest trans influence, is located trans to the open coordination site. The complexes appear to be stabilized by a weak agostic interaction of the metal with a ligand C-H bond positioned at the fourth-coordination site of the palladium center. The strength of the Pd…H bond, as assessed by tools of density functional theory, depended upon the donating properties of the ancillary ligands on palladium.

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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 syntheses, characterisation and crystal structure (when X = Br) of [Pd4(mu3-CF)(mu-X)3(PBut 3)4] (X = Cl, Br) are reported; the mu3-CF moiety is hydrogenated to CFH3 under mild conditions and serves as a model for the heterogeneous hydrogenation of CFCs to HCFCs.

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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 new method for the synthesis of substituted 2-acylallylmetal reagents in a highly regio- and stereoselective fashion involving a three-component assembly of allenes, acyl chlorides, and bimetallic reagents (B-B, Si-Si, and Sn-Sn) catalyzed by phosphine-free palladium complexes is described. Treatment of various allenes (CR2R3=C=CH2) with acyl chlorides (R1COCl) and bispinacolatodiboron in the presence of PdCl2(CH3CN)2 in toluene at 80 C gave 2-acylallylboronates CR2R3=C(COR1)CH 2B-(OCMe2CMe2O) in moderate to good yields. The acylsilation of allenes with acid chlorides and hexamethyldisilane (5) proceeded successfully in the presence of Pd(dba)2 in CH 3CN affording the corresponding allylsilanes (CR2R 3=C(COR1)CH2SiMe3) in good to moderate yields. Several chloroformates (R4OCOCl) also react with 1,1-dimethylallene (2a) and 5 to afford allylsilanes (CR2R 3=C(COOR4)CH2-SiMe3) in 66-70% yields. Acylstannation of allenes could also be achieved by slow addition of hexabutylditin (10) to the reaction mixture of acyl chloride (or chloroformate) and allene 2a in CH3CN in the presence of Pd(dba)2 at 60 C; the corresponding 2-substituted allylstannanes were isolated in moderate to good yields. The above catalytic reactions are completely regioselective and highly stereoselective. A mechanism is proposed to account for the catalytic reactions and the stereochemistry.

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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 diphosphine-phosphine oxide {[o-iPr2P(C6H 4)]2P(=O)H} (1) has been prepared, and its coordination to Ir and Pd has been explored. Using [IrCl(cyclooctene)2]2, the pincer hydride complex {(o-iPr2PC6H4) 2P(O)]IrHCl} (2) is readily obtained by phosphine-assisted P(O)-H bond activation. Coordination of CO to Ir affords the corresponding octahedral complex {(o-iPr2PC6H4)2P(O)] IrHCl(CO)} (3) as a single stereoisomer. The electronic properties of the PP(O)P ligand have been compared with those of related PEP frameworks on the basis of nuCO stretching frequencies. Treatment of 1 with [Pd(PtBu 3)2] gives the palladium hydride complex {(o-iPr 2PC6H4)2P(O)]PdH} (4). The mechanism of P(O)-H bond activation at Pd has been investigated computationally. Complex 4 reacts with methyl acrylate at room temperature, giving {(o-iPr 2PC6H4)2P(O)]PdCH(Me)CO 2Me} (7) as the result of regioselective insertion into the Pd-H bond.

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

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An unprecedented remote amide-directed palladium-catalyzed intermolecular highly selective benzylic C-H amination with N-fluorobenzenesulfonimide is developed, which represents the first direct benzylic C-H amination with a non-nitrene nitrogen source. This methodology provides a novel approach to circumvent the common ortho aromatic C-H selectivity in directed palladium catalyzed C-H functionalization.

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