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Diphosphines Possessing Electronically Different Donor Groups: Synthesis and Coordination Chemistry of the Unsymmetrical Di(N-pyrrolyl)phosphino-Functionalized dppm Analogue Ph2PCH 2P(NC4H4)2

The unsymmetrical diphosphinomethane ligand Ph2PCH 2P(NC4H4)2 L has been prepared from the reaction of Ph2P-CH2Li with PCl(NC4H 4)2. The diphenylphosphino group can be selectively oxidized with sulfur to give Ph2P(S)-CH2P(NC 4H4)2 1. The reaction of L with [MCl 2(cod)] (M = Pd, Pt) gives the chelate complexes [MCl 2(L-kappa2P,P?)] (2, M = Pd; 3, M = Pt) in which the M-P bond to the di(N-pyrrolyl)phosphino group is shorter than that to the corresponding diphenylphosphino group. However, the shorter Pd-P bond is cleaved on reaction of 2 with an additional 1 equiv of L to give [PdCl 2(L-k1P)2] 4. Complex 4 reacts with [PdCl 2(cod)] to regenerate 2, and with [Pd2(dba) 3]·CHCl3 to give the palladium(I) dimer [Pd 2Cl2(mu-L)2] 5, which exists in solution and the solid state as a 1:1 mixture of head-to-head (HH) and head-to-tail (HT) isomers. The palladium(II) dimer [Pd2Cl2(CH 3)2(mu-L)2] 6, formed by the reaction of [PdCl(CH3)(cod)] with L, also exists in solution as a mixture of HH and HT isomers, although in this case the HT isomer prevails at low temperature and crystallizes preferentially. Complex 6 reacts with TIPF6 to give the A-frame complex [Pd2(CH3)2(mu-Cl)(mu -L)2]PF6 7. The reaction of L with [RuCp*(mu 3-Cl)]4 leads to the dimer [Ru2Cp* 2(mu-Cl)2(mu-L)] 8, for which the enthalpy of reaction has been measured. The reaction of L with [Rh(u-Cl)(cod)]2 gives a mixture of compounds from which the dimer [Rh2(mu -Cl)(cod)2(mu-L)PF6 9 can be isolated. The crystal structures of 2·CHCl3, 3·CH2Cl2, 4, 5·1/4CH2Cl2, 6, 7·2CH2Cl 2, 8, and 9·CH2Cl2 are reported.

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

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Organocatalytic diboration involving “reductive addition” of a boron-boron-bond to 4,4?-bipyridine

A 4,4?-bipyridine-based catalyst system for diboration of pyrazine derivatives was established. The catalyst cycle consists of the following two steps: (1) reductive addition of the boron-boron bond of bis(pinacolato)diboron to 4,4?-bipyridine to form N,N?-diboryl-4,4?-bipyridinylidene and (2) oxidative boryl transfer from the intermediate to pyrazine to give N,N?-diboryl-1,4-dihydropyrazine with regeneration of 4,4?-bipyridine.

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

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XYLYL ISOCYANIDE PLATINUM AND PALLADIUM COMPLEXES

Bis(cycloocta-1,5-diene)platinum reacts with isopropyl isocyanide to give the trinuclear complex .A related palladium compound was prepared by treating either or with 2,6-dimethylphenyl isocyanide.Reactions of the cluster and its presumed palladium analogue with the olefins (NC)2C:C(CN)2, F2C:CFCl and (CN)2C:C(CF3)2, give the compounds (M=Pt, Pd) in which the metals are eta2-bonded to the coordinated olefins.The compound reacts with F2C:CFBr and with F2C:CFCl to give the traans complexes (X=Br, Cl).Similar compounds (M=Pt, Pd), (L=MeO2CHC:CHCO2Me, <*>OCH:CHCO<*>) have also been prepared, and characterised.Two platinum complexes <2> and (CNC6H3-2,6-Me2)4> have been synthesized by treating the complex with HSiMePh2 and cyclopropenone, respectively.NMR and IR data for the new species are reported and discussed.

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

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C60Pdn: The First Organometallic Polymer of Buckminsterfullerene

The organometallic polymer, C60Pdn, is prepared from C60 and a Pd0 precursor, and the palladium to C60 ratio (n) can be varied by thermal disproportionation.

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

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Heterotrimetallic M-M?-M? transition metal complexes based on 1,3,5-triethynylbenzene: Synthesis, solid state structure, and electrochemical and UV-vis characterization. EPR analysis of the in Situ generated associated radical cations

The synthesis of a series of complexes with different organometallic building blocks unsymmetrically arranged around the periphery of a 1,3,5-triethynylbenzene core is discussed. They are accessible by diverse consecutive reaction sequences, which allow the introduction of transition metal units such as Fc, [(tBu2bpy)(CO)3Re], [(eta5-C5H5)(Ph3P)2Ru], [(eta5-C5H5)(Ph3P) 2Os], and trans-[(Ph3P)2(Cl)Pt] (Fc = (eta5-C5H5)(eta5-C 5H4)Fe; tBu2bpy = 4,4?-di-tert-butyl-2,2?-bipyridyl). The solid state structures of five complexes have been determined. The electrochemical behavior of the newly synthesized mono-, heterobi-, and heterotrimetallic assemblies have been studied, showing that there is no significant electronic interaction between the respective metal atoms. UV-vis spectroscopic measurements suggest a weak interaction between the appropriate metal atoms. The associated radical cations were in situ generated by stepwise chemical oxidation and characterized by continuous wave electron paramagnetic resonance (EPR) investigations in X-band performed at low temperatures.

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

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Palladium-catalyzed allylic alkenylation of allylic alcohols with n-butyl acrylate

Various allylic alcohols reacted with n-butyl acrylate in the presence of p-toluenesulfonic anhydride and palladium catalysts to yield the corresponding n-butyl 2,5-dienoates with high regioselectivity.

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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’ll also look at important developments in the pharmaceutical industry because understanding organic chemistry is important in understanding health, medicine, the role of 52522-40-4, and how the biochemistry of the body works.Electric Literature of 52522-40-4

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New strategies for the synthesis of vitamin D metabolites via Pd-catalyzed reactions

The invention of new palladium-catalyzed reactions offers new insights into synthetic strategies directed toward the vitamin D system. The palladium-catalyzed cycloisomerization of 1,6- and 1,7-enynes to dialkylidenecycloalkanes permits a lynchpin approach to the A ring of vitamin Ds. Using the thioacetal of formaldehyde, the proper subunits containing the olefin and the acetylene were attached. Pd(2+) effected cycloisomerization to an A ring subunit. A more effective strategy evolved from the evolution of a Pd-catalyzed alkylative cyclization of enynes. Whereas prior work established the feasibility of this process for 1,6-enynes, model studies reported herein demonstrate the feasibility of its extension to 1,7-enynes. This reaction permits the creation of a new concept for vitamin D synthesis wherein A ring formation is concomitant with its attachment to an appropriate CD fragment. An asymmetric synthesis of the requistite 1,7-enyne required six steps. Bromomethylenation of Grundmann’s ketone and its side chain hydroxylated derivative proceeded with excellent geometrical selectivity (>30:1) using the Wittig reaction. A Pd catalyst generated from (dba)3Pd2·CHCl3 and triphenylphosphine stitched together these two units in a single step resulting in syntheses of alphacalcidiol and calcitriol.

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

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Sequential silylcarbocyclization/silicon-based cross-coupling reactions

A sequential rhodium-catalyzed silylcarbocyclization of enynes parlayed with a palladium-catalyzed, silicon-based cross-coupling reaction has been developed for the synthesis of highly substituted cyclopentanes. 1,6-Enynes reacted with benzyldimethylsilane in the presence of rhodium catalysts to afford five-membered rings bearing a (Z)-alkylidenylbenzylsilyl group. A variety of substitution patterns and heteroatom substituents were compatible. The silylcarbocyclization in which an unsaturated ester participated was also achieved. The resulting alkylidenylsilanes underwent palladium-catalyzed cross-coupling using tetra-n-butylammonium fluoride. This cross-coupling reaction displayed a broad substrate scope. A wide variety of substitution patterns, electronic properties, and heteroatoms were compatible. All of the cross-coupling reactions proceeded in high yields under very mild conditions and with complete retention of double bond configuration, resulting in densely functionalized 3-(Z)-benzylidenecyclopentanes and heterocycles.

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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 Preparative Method for alpha,beta-Unsaturated Nitriles by the Palladium-catalysed Decarboxylation-Dehydrogenation of Allyl alpha-Cyanocarboxylates

Allyl alpha-cyanocarboxylates, derived from cyanoacetic acid, were converted into alpha,beta-unsaturated nitriles in the presence of a palladium catalyst.

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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 kind of preparation b ( butyl phosphinethree uncles ) palladium (O) synthesis method (by machine translation)

The present invention provides a second ( butyl phosphinethree uncles ) palladium (O) in a high yield, low-cost synthetic process, with the three terafluoroborate butyl phosphinethree uncles (dibenzylidene acetone) two palladium (O) chloroform adduct, (1,5-cyclooctadiene) palladium dibromide reaction two kinds of divalent palladium compound, generated in the alkaline environment in the second ( butyl phosphinethree uncles ) palladium (O), the prior art expensive raw materials in producing the products, low yield, problem of harsh reaction conditions, the reaction yield of the method 50% or more. Has good generalization potential and application prospect. (by machine translation)

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