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Novel alkyne-bridged ferrocenophanes [fc{CO2(CH2)nC?}2] (2a: n = 2; 2b: n = 3) were synthesized from the corresponding terminal diacetylenic ferrocenes [fc{CO2(CH2)nC?CH}2] (1a: n = 2; 1b: n = 3) through ring-closing alkyne metathesis (RCAM) utilizing the highly effective molybdenum catalyst [MesC?Mo{OC(CF3)2CH3}3] (MoF6; Mes = 2,4,6-trimethylphenyl). The metathesis reaction occurs in short time with high yields whilst giving full conversion of the terminal alkynes. Furthermore, the solvent-dependant reactivity of 2a towards Ag(SbF6) is investigated, leading to oxidation and formation of the ferrocenium hexafluoroantimonate 4 in dichloromethane, whereas the silver(I) coordination polymer 5 was isolated from THF solution.

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

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Cyclometalation of bis(sulfoxide)-substituted m-xylene derivatives, rac / meso-1,3-(iPrS(O)CH2)2C6H4 , occurred readily with Pd(II) using two synthetic routes. The first route utilized [Pd(NCMe)4] [(BF4)2] as starting material and led to the exclusive isolation of the C2-symmetric diastereomer [rac-2,6-(iPrS(O)CH2)2C6H3 Pd(NCMe)][BF4], rac-3, even though spectroscopic measurements confirmed the formation of meso-3. The second palladation pathway used Pd(BF4)Cl(NCPh)2 and both diastereomers rac- and meso-2,6-(iPrS(O)CH2)2C6H3 PdCl, rac-and meso-4, were separable by fractional crystallization. Characterization of the isolated complexes using 1H and 13C NMR, FT-IR, and X-ray crystallography illuminated subtle differences between the two diastereomers of 4 and provided a rationale for the greater solution stability of rac-4 relative to meso-4. The source of the instability is due to the stereochemical configuration at sulfur. Additional solution studies, examined by variable-temperature 1H. NMR (25 to -130 C), probed the dynamic exchange behavior of the three complexes. In addition, electrospray mass spectrometry experiments of rac-4 in methanol solutions detected the presence of the unsupported mu-chloro-bridged dimer, [2,6-(iPrS(O)CH2))2C6H3Pd ]2-mu2-Cl.

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

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Both the conformation and flexibility of four mixed oxathia crown ethers and their Ag(I) and Pd(II) complexes were studied by 1H NMR (delta5, J, NOE, T1), 13C NMR, dynamic 1 NMR spectroscopy and molecular modelling. The stoichiometry and stability constants of the complexes were determined from corresponding Job’s plots in the case of Ag(I) complexes as the interchange between free and complexed states was fast on the NMR timescale; interchange for the Pd(II) complexes was sufficiently slow such that distinct sub-spectra were observable for the free and complexed states. In all cases where complexation was observed, 1:1 complexes were formed. Global minima structures determined from the modelling studies were analysed with respect to the barriers to ring interconversion, the flexibility of the species in solution and the preferred complexation of Ag(I) and Pd(II) to the sulfur atoms of the crown ethers.

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

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Chiral self-assembled macrocyclic Pd(II) and Cu(II) complexes with trans-chelation of n:n metal-bidentate P,N- and N,N-ligands have been designed toward the possibility of asymmetric Diels-Alder catalysis. Copyright

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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 CoRu2(dpa)4Cl2 (1) (dpa: 2,2?-dipyridylamide) is synthesized by the reaction of Ru2(OAc)4Cl and Co3(dpa)4Cl2. By mixing 1 with NH3, Co2+ can be removed and result in the formation of unique binuclear complex 4,0-Ru2(dpa)4Cl (2) featuring one coordination pocket supported by free pyridine groups. Hence, this complex can act as an outstanding precursor for the formation of heterotrimetallic chains with MRu2 cores. A series of M-Ru25+ complexes (M = Co2+ (3), Ag+ (4), Mn2+ (5), Fe2+ (6), Zn2+ (7), Cd2+ (8), Pd2+ (9), Rh2+ (10), and Ir2+ (11)) were prepared and isolated, representing the most complete series of heterotrimetallic chains to date. All these metal string complexes are in a linear trimetallic framework helically wrapped by four dpa- ligands, characterized by X-ray diffraction measurements. The bending of the trinuclear metal cores in RhRu2 (10) and IrRu2 (11) (?Ru-Ru-Rh: 167.58 and ?Ru-Ru-Ir: 167.61) indicates that a heterometallic metal-metal bonds (Ru-Rh; Ru-Ir) are generated. The studies from DFT calculation of 10 and 11 coincide with the experimental results. Furthermore, the M?Ru25+ distances are regulated by the factors including the bonding force of M-pyridyl and the static repulsion between M and Ru25+ unit. Interestingly, the trend for these distances is in line with that observed in trans-M(py)4Cl2 complexes.

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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 tricyclic bisamidines L1 and L2 are designed to be preconstrained so as to present synperiplanar donor sites for metal coordination. Their very different bite angles of 35 and 70 result from the incorporation of two five-membered instead of six-membered rings in their respective backbones. Distinct coordination preferences in a variety of metal complexes have now been confirmed by X-ray structural studies. While L1 afforded monodentate, symmetrical and unsymmetrical chelating as well as bimetallic bridging modes in its complexes, L2 has been found exclusively in a bidentate chelating mode.

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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 simple approach is described here for the in-place synthesis of polymer brushes by surface-initiated polymerization. A cyano-terminated self-assembled monolayer on a gold surface was used to anchor a highly active cationic Pd organometallic initiator by ligand exchange. We grew ultrasmooth patterned poly(4-methoxystyrene) brushes with excellent thickness control at room temperature. Copyright

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

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1,1′-Bis<(alkyl- or phenyl-)thio>– and 1,1′-bis(diphenylphosphino)-ferrocenes react with (CH3CN)4Pd(BF4)2 in the presence of triphenylphosphine to give 1/1 complexes in good yields.Spectral data have confirmed the presence of an Fe-Pd dative bond in these complexes.

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

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Novel strategies for the preparation of rigid cartwheel pincer metal complexes have been developed. The aromatic backbone of these materials ensures a high rigidity, which is expected to be important for a high retention when these multimetallic nanosize complexes are applied as homogeneous catalysts in a nanomembrane reactor. The ligand precursors C6[C6H3(CH2Y)2- 3,5]6 (10, Y = NMe2; 11, Y = SPh; 12, Y = PPh2; 13, Y = pz = pyrazol-1-yl) have been prepared in high yields from the key intermediate C6[C6H3 (CH2Br)2-3,5]6 (9). The hexakis(pincer) palladium(II) complexes C6[(PdX)-4-C6H2(CH2Y)2-3, 5]6 (14, Y = SPh, L = Cl; 15, Y = PPh2, L = Cl; 16, Y = pyrazol-1-yl, L = OAc; 17, Y = pyrazol-1-yl, L = Cl) have been prepared via direct electrophilic palladation of the corresponding ligands. The (tris)pincer ligand C6H3[Br-4-C6H3(CH2 NMe2)2-3,5]3-1,3,5 (20) was prepared via a triple-condensation reaction of 4-bromo-3,5-bis[(dimethylamino)methyl]acetophenone (19). Reaction of 20 with Pd(dba)2 yielded the tripalladium complex C6H3[(PdBr)-4-C6H3(CH2 NMe2)2-3,5]3-1,3,5 (21). The crystal structure of 21 shows a propeller-like structure with D3 symmetry and a fixed bromine-bromine distance of 17.4573(4) A, approximately forming a triangle with a height of 15.2 A. These nanosize cartwheel pincer metal complexes based on tridentate Y,C,Y? pincer ligands have been used as homogeneous Lewis-acid catalysts. Moreover, the influence of the donor substituent Y on the catalytic activity of cationic mono-Y,C,Y? PdII complexes as Lewis-acid catalysts in the double Michael reaction between methyl vinyl ketone and ethyl alpha-cyanoacetate, as a model reaction, has been investigated. It was found that cationic N,C,N?-type pincer complexes (1a, Y = NMe2; 1b, Y = pz; 1c, Y = pz* = 3,5-dimethylpyrazol-1-yl; 23) were superior to the P,C,P?- and S,C,S?-pincer complexes (1d, Y = PPh2-Le, Y = SPh). The nanosize cationic tri-N,C,N? PdII complex 23 was found to have a catalytic activity per catalytic site in the double Michael reaction of the same order of magnitude as the monopincer analogue 1a (k = 279 × 10-6 s-1 for 1a vs k = 232 × 10-6 s-1 for 23). The combination of the nanosize dimensions, the catalytic activity, and the high thermal and air stability makes these complexes excellent candidates for application in a continuous process in a nanomembrane reactor.

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

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Double acylation of alkenes such as norbornene and vinyl-silane proceeds by the use of acylchromate complexes and a cationic Pd(II) complex. When two different acylchromates are added successively to a mixture of alkene and the Pd complex, unsymmetrical diketones are obtained almost selectively.

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