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The new rhenium-tin complex Re2(CO)8(mu-SnPh2)2, 1 was obtained in 52% yield from the reaction of Re2(CO)8(mu-H)[mu-C(H)C(H)Bu] with Ph3SnH. Compound 1 contains two SnPh2 groups bridging a long Re-Re single bond, Re-Re = 3.1971(4) A [3.1902(4) A], Re-Sn = 2.7429(4) A [2.7445(4) A], and 2.7675(4) [2.7682(5) A]. A bis-Pd(PBut3) adduct of 1, Pd2Re2(CO)8(mu-SnPh2)2(PBut3)2, 2 was obtained from the reaction of 1 with Pd(PBut3)2. Compound 2 contains Pd(PBut3) groups bridging two of its four Re-Sn bonds. The Re-Re bond and the unbridged Re-Sn bonds in 2 are significantly longer than those in 1, 3.245(1) A and 2.8167(14) A, respectively. Fenske-Hall molecular orbital calculations on 1 and 2 have been performed to explain the metal-metal bonding in these unusual mixed-metal polynuclear metal complexes. 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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We report a palladium-catalyzed carbon-carbon bond-forming reaction between aryl iodides and alkenes. In contrast to traditional cross-coupling reactions, two new bonds are formed, and all of the atoms in the starting materials are incorporated into the product. The use of a palladium catalyst with bulky phosphine ligands is found to be crucial for reactivity.

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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 compounds HM(CO)4SnPh3, M = Os (10), Ru (11) are activated in the presence of Pt-(PBut3)2 and Pd(PBut3)2 toward the insertion of PhC 2H into the M-H bond. The compounds PtOs(CO)4-(SnPh 3)(PBut3)[mu-HCC(H)Ph], 12, and PtOs(CO) 4(SnPh3)(PBut3)[mu-H 2CCPh], 13, were obtained from the reaction of 10 with PhC 2H in the presence of Pt(PBut3)2. Compounds 12 and 13 are isomers containing alkenyl ligands formed by the insertion of the PhC2H molecule into the Os-H bond at both the substituted and unsubstituted carbon atoms of the alkyne. Both compounds contain a Pt(PBut3) group that is bonded to the osmium atom and a bridging alkenyl ligand that is pi-bonded to the osmium atom. The reaction of 11 with PhC2H in the presence of Pt(PBut 3)2 yielded the products PtRu(CO)4(SnPh 3)(PBut3)[mu-HC2(H)Ph], 14, and PtRu(CO)4(SnPh3)(PBut3)[mu-H 2C2Ph], 15, which are also isomers similar to 12 and 13. The reaction of 11 with PhC2H in the presence of Pd(PBu t3)2 yielded the product PdRu(CO) 4(SnPh3)(PBut3)[mu-H 2C2Ph], 16. Compound 16 contains a Pd(PBut 3) group bonded to the ruthenium atom and a bridging H 2C2Ph ligand that is pi-bonded to the palladium atom. Compound 10 reacted with Pt(PBut3)2 in the absence of PhC2H to yield the compound PtOs(CO)4(SnPh 3)(PBut3)(mu-H), 17. Compound 17 is a Pt(PBut3) adduct of 10. It contains a Pt-Os bond with a bridging hydrido ligand. Compound 17 reacted with PhC2H to yield 12. Compound 12 reacted with PhC2H to yield the compound PtOs(CO) 3(SnPh3)(PBut3)[mu-HCC(Ph)C(H)C(H) Ph], 18. Compound 18 contains a bridging 2,4-diphenylbutadienyl ligand, HCC(Ph)C(H)C(H)Ph, that is pi-bonded to the osmium atom and sigma-bonded to the platinum atom. Fenkse-Hall molecular orbitals of 17 were calculated. The LUMO of 17 exhibits an empty orbital on the platinum atom that appears to be the most likely site for PhC2H addition prior to its insertion into the Os-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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Take five: A new method employing aryl halide carbonylation to directly access heterocycles has been described (see scheme). In a single palladium-catalyzed reaction the catalyst mediates two consecutive carbonylation steps, thereby converting five components (aryl iodide, two units imine, and two units CO) into an imidazoline ring.

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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 compounds Pd(eta3-1-Ph-C3H4) (eta5-C5H5) (I), Pd2(dba) 3 (II), Pd(OAc)2 (III), and [Pd(eta3-1-Ph- C3H4)Cl]2 (IV) are frequently utilized as catalyst precursors for a variety of cross-coupling processes, including Suzuki-Miyaura, Heck-Mizoroki, Sonogashira, and Buchwald-Hartwig reactions. In the preceding paper in this issue, we assess and compare catalyst systems based on I-IV activated with PBut3, XPhos, and/or Mor-Dalphos for the prototypical Buchwald-Hartwig amination reactions of 4-bromo- and 4-chloroanisole with morpholine, noting several apparent incongruities which seem to indicate mechanistic dissimilarities for various reactant/precatalyst combinations. In this paper we investigate by NMR spectroscopy the solution chemistry of I and IV with PBut3, XPhos, and Mor-Dalphos, noting similarities and differences in the respective abilities of these precursor-ligand combinations to generate palladium(0) catalyst systems. We find inter alia that steric requirements prevent Xphos and Mor-Dalphos from forming 2:1 palladium(0) complexes and, surprisingly, that 1:1 palladium(0) complexes of Xphos and Mor-Dalphos are unstable with respect to dissociation to free ligand and palladium metal. In other words, these two ligands and, by implication, other sterically demanding phosphine ligands do not form palladium(0) 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 one-pot reaction that directly converts dihydrosilanes into silyl ethers of tertiary silanes is reported. Under palladium catalysis, one Si?H bond of the dihydrosilane formally engages in C(sp3)?Si bond formation with a vinyl iodide while the other Si?H bond is transformed into a silyl iodide that undergoes facile alcoholysis with an alcohol. The C?C double bond is reduced in that process. This three-component reaction provides in a single synthetic operation an access to silyl ethers of functionalized and hindered alcohols. Several of those would otherwise be difficult to make but the intermediacy of a highly reactive silyl iodide even allows for tert-butanol to react at room temperature.

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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 efficient new formal insertion strategy via combination of reductive elimination and oxidative addition sequence was reported, in which the transient N-acyliminium ions formed via hydrocarbonylation function as key intermediates. This strategy has enabled a novel palladium-catalyzed hydrocarbonylative cyclization of azaarene-tethered alkenes or dienes via sequential insertion of a Ca? C bond, CO, and a Ca? N bond into palladium-hydride bonds. This method provides a new and highly efficient synthetic approach to quinolizinones and its derivatives with extended I-conjugated systems, possessing tunable emission wavelengths and good photoluminescence capabilities.

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

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Reactions of chelating pincer-type PNP ligands based on the bis(ortho-phosphinoaryl)-amine substructure and containing either an N-H (PN(H)P, 1) or N-Me (PN(Me)P, 2) central moiety with group 10 complexes have been explored. Reactions with MCl2 (MCl2 = NiCl 2, (COD)PdCl2, (COD)PtCl2, COD = 1,5-cyclooctadiene) proceed readily with the loss of either HCl or MeCl and the formation of (PNP)MCl (7) where PNP is an anionic, meridional amido-PNP ligand. Alkylation of (PNP)MeCl with MeMgCl gives (PNP)MMe (9), and reaction of (PNP)MCl with excess NaBH4 provides (PNP)MH (8). (PNP)MH (8) compounds react with CDCl3 to regenerate (PNP)MCl (7). The transformations 7 – 8 – 7 – 9 are sluggish for M = Pt compared with M = Ni or Pd. Solid-state structures of (PNP)PdH (8b-Pd) and (PNP)-PdMe (9b-Pd) were determined. The environment about Pd in either structure is approximately square planar with a meridional amido-PNP ligand. Reactions of 1 and 2 with LnM0 (L n = (COD)2, (PPh3)4, (PBu 13)2) proceed in some cases via N-H or N-C oxidative addition to give either (PNP)MH (8) or (PNP)MMe (9). The N-H oxidative addition reactions are more facile. Both the N-H and N-Me oxidative addition reactions are kinetically inhibited by liberated phosphines from the LnM0 starting material. Thermolysis of (PNP)MMe (9, M = Ni, Pd, Pt) in the presence of excess PPh3 does not lead to N-C reductive elimination, thus indicating irreversibility of the N-C oxidative addition.

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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 disclosure relates to amine-based compounds and organic light emitting devices is fixed to the body. (by machine translation)

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

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[Problem] To provide a compound that has an intestinal phosphate transporter (NPT-IIb) inhibitory action and is useful as an active ingredient of an agent for treating and/or preventing hyperphosphatemia. [Means for Solution] The present inventors conducted thier studies on a compound that has an NPT-IIb inhibitory action and is useful as an active ingredient of an agent for treating and/or preventing hyperphosphatemia. As a result, they created an aminoalkyl-substituted N-thienylbenzamide derivative which has NPT-IIb inhibitory action, thereby completing the present invention. The aminoalkyl-substituted N-thienylbenzamide derivative of the present invention has an NPT-IIb inhibitory action and can be used as an agent for preventing and/or treating hyperphosphatemia.

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