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Well-Defined Rhodium-Gallium Catalytic Sites in a Metal-Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes

Promoters are ubiquitous in industrial heterogeneous catalysts. The wider roles of promoters in accelerating catalysis and/or controlling selectivity are, however, not well understood. A model system has been developed where a heterobimetallic active site comprising an active metal (Rh) and a promoter ion (Ga) is preassembled and delivered onto a metal-organic framework (MOF) support, NU-1000. The Rh-Ga sites in NU-1000 selectively catalyze the hydrogenation of acyclic alkynes to E-alkenes. The overall stereoselectivity is complementary to the well-known Lindlar’s catalyst, which generates Z-alkenes. The role of the Ga in promoting this unusual selectivity is evidenced by the lack of semihydrogenation selectivity when Ga is absent and only Rh is present in the active site.

Well-Defined Rhodium-Gallium Catalytic Sites in a Metal-Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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The ?-Bonded Palladium(II) Complex of tetraphenylcyclobutadienecobalt(I)

tetraphenylcyclobutadienecobalt(I) reacts with lithium tetrachloropalladate(II) in the presence of sodium acetate to give an ortho-palladated binuclear complex.The ?-bonded structure of the complex was confirmed by studies of the IR and 1H-NMR spectra and of the reactions with triphenylphosphine, thalium(I) acetylacetonate, and lithium aluminum deuteride.The reactions of the ?-bonded complex with carbon monoxide and olefins have been examined.

The ?-Bonded Palladium(II) Complex of tetraphenylcyclobutadienecobalt(I)

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Nickel(0)-Catalyzed Hydroalkenylation of Imines with Styrene and Its Derivatives

A nickel(0)-catalyzed hydroalkenylation of imines with styrene and its derivatives is described. A wide range of aromatic and aliphatic imines directly coupled with styrene and its derivatives, thus providing various synthetically useful allylic amines with up to 95 % yield. The reaction offers a new atom- and step-economical approach to allylic amines by using alkenes instead of alkenyl-metallic reagents. Experiments and DFT calculations showed that TsNH2 promotes the proton transfer from the coordinated olefin to the imine, accompanied by a new C?C bond formation.

Nickel(0)-Catalyzed Hydroalkenylation of Imines with Styrene and Its Derivatives

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Substituent effects of phosphonate groups electronic repartition of pi-conjugated ferrocene analogues of stilbene

The synthesis of para-substituted ferrocene analogues of stilbene was performed by using the Heck reaction, starting from vinylferrocene. The variation of the electronic density of these compounds with the electronic withdrawing strength of the substituents was studied using 13C NMR spectroscopy, absorption spectra and cyclic voltammetry. The correlation of Hammett constants with the redox properties of the substituted compounds using Nagy’s method allowed us to revisit the determination of the Hammett constants of diethyl phosphonate ester and phosphonic acid substituents. Our measurements were in agreement with the literature except for the diethyl phosphonate group.

Substituent effects of phosphonate groups electronic repartition of pi-conjugated ferrocene analogues of stilbene

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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1-Ferrocenylcyclopropene and 1-ferrocenylcyclopropyl cation

Dehydrobromination of cis and trans isomers of 1-bromo-2-ferrocenylcyclopropanes affords 1-ferrocenylcyclopropene. Its protonation with HBF4 results in 1-ferrocenylcyclopropylium tetrafluoroborate, which alkylates N,N-dimethylaniline in para position to yield 1-(p-dimethylaminophenyl)-1-ferrocenylcyclopropane. 1-Ferrocenylcyclopropene reacts with 1,3-diphenylisobenzofuran to give the classical [4+2]-cycloaddition product. Its structure as exo-2-ferrocenyl-1,5-diphenyl-6,7-benzo-8-oxatricyclo [3.2.1.02.4]oct-6-ene was established based on the data from X-ray diffraction analysis.

1-Ferrocenylcyclopropene and 1-ferrocenylcyclopropyl cation

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Ferrocenyl thioesters

Ferrocenyl thiols of the formula STR1 wherein n is an integer of from 2 to 4 are prepared by reacting a compoundf the formula STR2 with thioacetic acid, STR3 at elevated temperatures in the presence of a free radical initiator to produce a thiol ester of the formula STR4 and then hydrolyzing the thiol ester to produce the thiol. The thiols are useful as non-migrating burning rate modifiers for unsaturated rubber-based propellants.

Ferrocenyl thioesters

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Redox behaviour of ferrocene derivatives VIII 1,1?-bis(diphenylphosphino) ferrocenes

A study has been made of the possibility of increasing the stability of the 1,1?-bis(diphenylphosphino)ferrocenium monocation by introduction of appropriate substituents into the cyclopentadienyl ligands. The electrochemical behaviour of a series of 1,1?-bis(diphenylphosphino)ferrocenes bearing substituents with a range of electronic properties has been examined. The results reveal that, the higher the electron-donating ability of the substituents, the longer is the lifetime of the corresponding 1,1?-bis(diphenylphosphino)ferrocenium monocation. However, no stable ferrocenium cation has been obtained; mass spectrometry shows that mixtures of mono- and di-bis(diphenylphosphine)oxides are ultimately formed as products resulting from decomposition of the initially electrogenerated 1,1?-bis(diphenylphosphino)ferrocenium species.

Redox behaviour of ferrocene derivatives VIII 1,1?-bis(diphenylphosphino) ferrocenes

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Facile regio- and stereoselective hydrometalation of alkynes with a combination of carboxylic acids and group 10 transition metal complexes: Selective hydrogenation of alkynes with formic acid

A facile, highly stereo- and regioselective hydrometalation of alkynes generating alkenylmetal complex is disclosed for the first time from a reaction of alkyne, carboxylic acid, and a zerovalent group 10 transition metal complex M(PEt3)4 (M = Ni, Pd, Pt). A mechanistic study showed that the hydrometalation does not proceed via the reaction of alkyne with a hydridometal generated by the protonation of a carboxylic acid with Pt(PEt 3)4, but proceeds via a reaction of an alkyne coordinate metal complex with the acid. This finding clarifies the long proposed reaction mechanism that operates via the generation of an alkenylpalladium intermediate and subsequent transformation of this complex in a variety of reactions catalyzed by a combination of Bronsted acid and Pd(0) complex. This finding also leads to the disclosure of an unprecedented reduction of alkynes with formic acid that can selectively produce cis-, trans-alkenes and alkanes by slightly tuning the conditions.

Facile regio- and stereoselective hydrometalation of alkynes with a combination of carboxylic acids and group 10 transition metal complexes: Selective hydrogenation of alkynes with formic acid

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Synthesis, structure, electrochemistry and ROMP-activity of new ferrocenyl analog of Grubbs’ metathesis catalyst

Treatment of [(PCy3)2Cl2Ru=CH-Ph] (I) with vinylferrocene 1 and 1-ferrocenyl-1,3-butadiene 2 yielded solid products. These new complexes were characterized by 1H NMR, 31P NMR and 13C NMR spectroscopy. X-ray crystal structures of both the complexes have been solved. The crystal structure of II confirmed the assigned structure and revealed existence of two sets of intermolecular C-H-Cl(M) type interactions, viz. (Ru)Cl-H-C(ferrocene) and (Ru)Cl-H-CHCl2. The air-stable, dark solid II is an efficient catalyst for ring-opening metathesis polymerization (ROMP) of cyclopentene, norbornene and cycloocta-1,5-diene. Electrochemical behavior of the complexes clearly reflects electronic communication between two metal centers.

Synthesis, structure, electrochemistry and ROMP-activity of new ferrocenyl analog of Grubbs’ metathesis catalyst

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Ferrocene conjugated oligonucleotide for electrochemical detection of DNA base mismatch

We describe the synthesis, binding, and electrochemical properties of ferrocene-conjugated oligonucleotides (Fc-oligos). The key step for the preparation of Fc-oligos contains the coupling of vinylferrocene to 5-iododeoxyuridine via Heck reaction. The Fc-conjugated deoxyuridine phosphoramidite was used in the Fc-oligonucleotide synthesis. We show that thiol-modified Fc-oligos deposited onto gold electrodes possess potential ability in electrochemical detection of DNA base mismatch.

Ferrocene conjugated oligonucleotide for electrochemical detection of DNA base mismatch

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion