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One with the surface: A method is presented for electrode modification with terminal alkynes and alkenes. Direct oxidation of these moieties leads to efficient grafting onto glassy carbon, gold, platinum, and indium tin oxide surfaces. Various ferrocenes and 5,10,15,20-(4-ethynylphenyl)porphyrin were attached in this way. Copyright

Covalent attachment of porphyrins and ferrocenes to electrode surfaces through direct anodic oxidation of terminal ethynyl groups

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Reference£º
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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Alkoxymethylation of ferrocenylalkenes

The reaction of ferrocenylalkenes with chloromethyl alkyl ethers catalyzed by Lewis acids gives 3-alkoxy-1-ferrocenyl carbocations, which can be trapped by nucleophiles to give 1,3-disubstituted ferrocenylalkane derivatives.The application of this reaction to the preparation of chiral 3-hydroxy-1-ferrocenylalkylamines is described; their structures and conformations have been elucidated by NMR spectroscopy.The stereochemical course of the alkoxymethylation reaction involves “exo” attack of the chloromethyl ether at the beta carbon of the double bond relative to the ferrocene, and subsequent “exo” attack of the nucleophile at the carbocationic centre formed in the first step.

Alkoxymethylation of ferrocenylalkenes

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Reference:
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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Synthesis and applications of tricarbonyliron complexes of dendralenes

[3]Dendralene and [4]dendralene are converted smoothly into tricarbonyliron complexes. The structures of four complexes analyzed by DFT and single-crystal X-ray analysis show that, in contrast to free hydrocarbons, complexed dendralenes prefer a roughly in-plane conformation. The complexes are stable towards Fe(CO)3 group migration up to 150 C. The synthetic value of Fe(CO)3 complexation in the dendralene series is demonstrated through a variety of selective synthetic manipulations (Diels-Alder reaction, dipolar cycloaddition, Simmons-Smith cyclopropanation, dihydroxylation, olefin cross metathesis) that are not achievable by direct transformation of the free hydrocarbons. Application to the synthesis of a previously unreported, highly reactive linear/cross-conjugated hydrocarbon is also described. Simplicity through complexation: Tricarbonyliron complexes of dendralenes are readily prepared and stable. They allow the formation of products that cannot be accessed directly from dendralenes, including unprecedented structures (see scheme).

Synthesis and applications of tricarbonyliron complexes of dendralenes

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Reference:
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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Unidirectional Current Flow and Charge State Trapping at Redox Polymer Interfaces on Bilayer Electrodes: Principles, Experimental Demonstration, and Theory

Bilayer electrodes consist of conductive electrodes coated with or bonded to two physically discrete polymeric layers which contain two different redox substances having different E0′ values.The redox substance in the inner polymeric film next to the electrode can be oxidized or reduced by the electrode.That in the outer polymer film is constrained, by physical isolation from the electrode, to undergo oxidation or reduction only at electron energies for redox conductivity by the inner film.This arrangement leads to rectified (unidirectional) current flow.Experimental results from bilayer electrodes based on nine different combinations of redox substances in the films are presented to demonstrate the generality of the phenomenon and the ability to fabricate bilayer film.The redox substances include fixed-site redox polymers like poly2+, polyvinylferrocene, poly(4-methyl-4′-vinyl-N,N’-ethylene-2,2′-bipyridinium), and siloxane polymer of N-methyl-N”-(4-(2-(trimethylsilyloxy)ethyl)benzyl)-4-4′-bipyridinium, and (inner film) mobile redox sites like bromide, hexachloroiridate, and benzophenone.Various mechanisms are considered for bilayer electrode nonidealities which appear as a leakage of redox state trapped in the outer film, an a theory describing voltammeric properties of bilayer electrodes is compared to experimental results.

Unidirectional Current Flow and Charge State Trapping at Redox Polymer Interfaces on Bilayer Electrodes: Principles, Experimental Demonstration, and Theory

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Reference:
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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Application of 1271-51-8, Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps.In an article, 1271-51-8, molcular formula is C12H3Fe, belongs to iron-catalyst compound, introducing its new discovery.

PHOTOINDUCED REACTIONS OF ORGANIC COMPOUNDS WITH TRANSITION METAL COMPLEXES IV. THERMAL AND PHOTOCHEMICAL REACTIONS OF PtCl62- AND PtCl42- WITH OLEFINS AND ALCOHOLS: CONVENIENT SYNTHESIS OF ?-OLEFIN COMPLEXES OF PLATINUM(II)

Olefinplatinum(II) ?-complexes can be synthesized by the following methods: (i) heating a solution of an olefin, alcohol or alkyl acetate and PtCl62- in acetic acid; (ii) light irradiation of a solution of PtCl62- and an olefin in acetone, and (iii) light irradiation of a solution of PtCl42- and an olefin in aqueous acetone.The possible mechanisms of the thermal and photoinduced reactions are discussed.

PHOTOINDUCED REACTIONS OF ORGANIC COMPOUNDS WITH TRANSITION METAL COMPLEXES IV. THERMAL AND PHOTOCHEMICAL REACTIONS OF PtCl62- AND PtCl42- WITH OLEFINS AND ALCOHOLS: CONVENIENT SYNTHESIS OF ?-OLEFIN COMPLEXES OF PLATINUM(II)

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Reference:
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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Poly(vinyl ferrocene) redox behavior in ionic liquids

We describe in this report a systematic electrochemical characterization of the ion-solvent coupling mechanisms of poly(vinyl ferrocene) (PVF) in pure ionic liquid (IL) and 0.1 M IL aqueous solutions. Our study showed that the unique solvation and ionic properties of ILs significantly affected the break-in process and the ion-solvent transport mechanisms of PVF redox switching. A square model that emphasized both faradaic and nonfaradaic processes of PVF was used to explain the unique irreversible break-in effect in the pure ILs. The electrochemical quartz crystal microbalance technique was used to characterize the PVF redox processes in 0.1 M 1-butyl-3-methyl imidazolium tetrafluoroborate and 0.1 M methanesulfonate ILs in which an obvious difference of cyclic voltammogram was observed. Our results suggested the existence of strong IL-polymer interaction in 0.1 M methanesulfonate IL solutions, i.e., not only the anions but also the IL molecules interacted with the PVF matrix. The cations were later removed from the PVF matrix to balance the excessive positive charge in PVF oxidation. Our study confirmed that IL was not only an electrolyte but also a solvent in PVF redox switching processes. Various types of interactions between PVF and the IL, including dispersion, dipole induction, dipole orientation, hydrogen-bonding, or ionic/charge-charge interactions, could significantly change the PVF redox dynamics. Thus, IL tremendous diversity in structural and chemical properties and their distinctive properties offer us an excellent opportunity to explore IL-polymer interactions and to dynamically control the conductive polymer relaxation processes and their redox switching mechanism for various applications.

Poly(vinyl ferrocene) redox behavior in ionic liquids

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Reference:
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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FORMATION OF ETHYNYL METALLOCENYL KETONE FROM 1,1,1-TRICHLORO-3-ALKOXY-3-METALLOCENYLPROPANE

1,1,1-Trichloro-3-ethoxy-3-ferrocenylpropane (1a) gives ethynyl ferrocenyl ketone (2a) via an unusual elimination of hydrogen chloride, when 1a is treated with alkali and then acid.The ruthenium analog (1b) also affords ethynyl ruthenocenyl ketone (2b).No migration of the side chain is involved in this process.

FORMATION OF ETHYNYL METALLOCENYL KETONE FROM 1,1,1-TRICHLORO-3-ALKOXY-3-METALLOCENYLPROPANE

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Reference:
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

 

Brief introduction of Vinylferrocene

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Ion exchange of ferro(ferri)cyanide in polyvinylferrocene films

Ion exchange of ferro/ferricyanide into oxidized polyvinylferrocene (PV-Fc) films occurs upon repetitious cycling of a PV-Fc film between its oxidized and reduced forms in the presence of either Fe(CN)63- and Fe(CN)64-. The ion exchange is evident from cyclic voltammetry and the response of a quartz crystal microbalance coated with a PV-Fc film. Insertion of the multiply charged anions appears to result in deactivation of polyvinylferrocene sites, with the exchanged films initially exhibiting voltammetric waves due to confined ferro(ferri)cyanide. Prolonged cycling of the exchanged films causes complete passivation of the films towards redox species in the film, as well as solution species, suggesting extensive electrostatic cross-linking by the multiply charged anions. Coulometric experiments suggest that approximately one ferro(ferri)cyanide exchanges for three PV-Fc redox sites. The visible spectra of the exchanged films after prolonged cycling suggests the presence of prussian blue-like species in the polymer film which presumably arise from decomposition of the polymer.

Ion exchange of ferro(ferri)cyanide in polyvinylferrocene films

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Reference:
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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In heterogeneous catalysis, catalysts provide a surface to which reactants bind in a process of adsorption. In homogeneous catalysis, catalysts are in the same phase as the reactants. Application In Synthesis of Vinylferrocene. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 1271-51-8, Name is Vinylferrocene

Ferrocenyl-naphthalimide donor-acceptor dyads with aromatic spacer groups

The preparation and characterization of a series of dyads containing ferrocene donor and naphthalimide acceptor units, separated by aromatic spacer groups, are reported. The compounds contain a ferrocene-ethenyl spacer component linked to the 4-position of a naphthalimide by an ethynyl bridge, Fc-CH=CH-spacer-C?C-naphthalimide (Fc = ferrocenyl), where the spacers are 1,4-phenyl, 4,4?-biphenyl, and 9,10-anthryl. Precursors to the dyad systems, halo-spacer-C?C-naphthalimide, are also characterized where the halo-spacers are 1-bromophenyl, 4-bromobiphenyl, and 9-iodoanthryl. Various synthetic strategies are examined, with attachment of the spacer to 4-ethynylnaphthalimide followed by reaction with ethenylferrocene proving the most effective route. Crystal structures of the donor-spacer-acceptor (D-S-A) compound (E)-1-ethenylferrocenyl-4-(4-ethynyl-N-methyl-1,8-naphthalimide)benzene (7) and the precursor compounds (E)-4-bromo-4?-(ethenylferrocenyl) biphenyl (2) and 4-ethynyl-4?-(4-ethynyl-N-methyl-1,8-naphthalimide) biphenyl (4) are reported, with packing in the two naphthalimide derivatives dominated by offset pi-stacking interactions. Compounds containing the ferrocenyl groups show the anticipated one-electron oxidation processes at potentials that vary little with the spacer groups. Both the ferrocenyl derivatives and their naphthalimide precursors show reversible reduction waves. The single wave for the phenyl and biphenyl compounds and their precursors is assigned to reversible one-electron reduction of the naphthalimide unit. The corresponding anthracene derivatives display two reversible reductions associated with the naphthalimide and the anthryl moieties, respectively.

Ferrocenyl-naphthalimide donor-acceptor dyads with aromatic spacer groups

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Reference:
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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Efficient regio- and diastereo-controlled synthesis of 1,1?- and 1,1?,2,2?-functionalised ferrocenes and the formation of 2-oxa[3]ferrocenophanes

The synthesis of a C2 symmetric 1,1? ,2,2?-tetrasubstituted ferrocene system was discussed. The route involved the reduction of ferrocenyl carbonyl compounds which gave access to a range of alcohols, alkenes, alkanes, ethers, and 2-oxa[3]ferrocenophanes depending on the precise conditions used. The loss of optical activity of 1,1?-bis(hydroxymethyl)ferrocenes and 1,1?-bis(hydroxymethyl)ruthenocenes, which had been prepared by asymmetric reduction, was demonstrated in an acidic medium by extensive 1H NMR studies.

Efficient regio- and diastereo-controlled synthesis of 1,1?- and 1,1?,2,2?-functionalised ferrocenes and the formation of 2-oxa[3]ferrocenophanes

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Reference£º
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