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Synthesis, structure, and redox chemistry of ethenyl and ethynyl ferrocene polyaromatic dyads

A series of ferrocenyl-arene dyads, Fc-C=C-Ar, trans-Fc-CH=CH-Ar, and Fc-CH=CH-CH=CH-Ar (Ar = phenyl, 1-naphthyl, 2-naphthyl, 9-phenanthryl, 9-anthryl, 1-pyrenyl, 3-perylenyl) have been synthesized. Their structures and spectroelectrochemical properties are discussed. The molecular structures of several have been determined by X-ray diffraction and the observed structures compared with global free-energy minimized calculated structures. In the solid state all ethynyl dyads have the aromatic ring orthogonal to the ferrocenyl cyclopentadienyl rings, whereas calculations predict a coplanar orientation. Calculated and observed structures agree for the ethenyl dyads with the rings orthogonal and coplanar for the anthryl and pyrenyl dyads, respectively. In most cases the solid-state structures are stabilized by offset pi-stacking interactions between the polycyclic hydrocarbon rings. The two bands in the electronic spectra of the neutral dyads are due to the individual aryl and ferrocenyl end-groups. Upon oxidation at the [Fc]+/0 couple, the ferrocenyl transition is replaced by LMCT bands at lower energy and a new weak band in the NIR assigned to a Fc+ ?aryl transition; these assignments are supported by resonance Raman spectra, and the energy of the Fc+? aryl transition correlates with the ionization energy of the aryl group. These are therefore electrochromic dyads.

Synthesis, structure, and redox chemistry of ethenyl and ethynyl ferrocene polyaromatic dyads

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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

 

Archives for Chemistry Experiments of Vinylferrocene

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Inclusion complexes of ferrocenes and beta-cyclodextrins. Critical appraisal of the electrochemical evaluation of formation constants

We report the results of a systematic electrochemical study of the host-guest supramolecular adducts between ferrocene (Fc), ferrocenium cation (Fc+), and other mono- and disubstituted ferrocene derivatives with different beta-cyclodextrins (CD) in mixed organic-aqueous media. The influence on the formation constants (Kf) of the organic cosolvent, the different substituents on Fc, and the type of CDs are evaluated. NMR and conductometry responses of ferrocenium cation solutions in the presence of CD confirm the weak propensity of Fc+ to enter into the cyclodextrin cavity. The Kf value generally decreases as the steric bulk and the rigidity of Fc substituents increases, consistent with an inclusion model in which the Fc fits into the CD cavity in an axial mode while the substituent protrudes out. Interestingly, the addition of sulfated beta-CD shifts the redox Fc/Fc+ couple toward cathodic values, indicating that the oxidized, cationic form Fc+ is more strongly bound to the sulfated cyclodextrin than neutral Fc, probably by means of electrostatic interaction with the external -SO3- functionalities.

Inclusion complexes of ferrocenes and beta-cyclodextrins. Critical appraisal of the electrochemical evaluation of formation constants

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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

 

Brief introduction of Vinylferrocene

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Measurement of double-layer forces at the polymer film/electrolyte interfaces using atomic force microscopy: Concentration and potential-dependent interactions

The forces between colloidal probes and several polymer films were measured by atomic force microscopy in the presence of a series of electrolyte solutions. For Nafion films using a negatively charged silica tip, a repulsive force was obtained at different concentrations of NaClO4. A similar result was obtained for an anion exchange membrane with a positively charged probe. Derjaguin-Landau-Verwey-Overbeek (DLVO) theory was employed to calculate the surface potential and hence, the surface charge. The surface charge density (a??0.3I?C/cm2) was independent of electrolyte concentration. The slope for plot of potential drop vs In[cs] was a??0.020 V. A theoretical treatment based on GCS theory was employed to account for the above results. For a poly(vinylferrocene) (PVF) film, potential-dependent force curves were obtained, which were qualitatively different from that previously reported for an electronically conducting polymer film electrode.

Measurement of double-layer forces at the polymer film/electrolyte interfaces using atomic force microscopy: Concentration and potential-dependent interactions

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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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Rhodium(I)-catalysed alkylation of 2-vinylpyridines with alkenes as a result of C-H bond activation

2-Vinylpyridines undergo regioselective beta-alkylation with alkenes in the presence of a rhodium(I) complex as a catalyst to give products resulting from an anti-Markownikoff reaction. These results show the feasibility of alkylation of an alkenic position as a result of C-H bond activation. 2-(Prop-1-en-2-yl)pyridine 1 and 1-phenyl-1-(2-pyridyl)ethylene 15 react with linear terminal alkenes to give the corresponding alkylated products in high yields. Cyclic alkenes, allyl alcohol, but-3-en-1-ol and methyl vinyl ketone, however, fail to react with 1. Pent-2-ene gives the linear alkylated product in low yield. 6-Methyl-2-vinylpyridine 24 and 2-vinylpyridine 32 give the alkylated products in low yield together with their dimeric products. The alkenic C-H bond of 2-(cyclohex-1-enyl)pyridine 36 has been regioselectively alkylated. 2-(Cyclohex-1-enyl)pyridine 36 with alkenes in the presence of the RhI catalyst undergoes regiospecific alkylation at the alkenic position.

Rhodium(I)-catalysed alkylation of 2-vinylpyridines with alkenes as a result of C-H bond activation

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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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Methylenespiro[2.3]hexanes via Nickel-Catalyzed Cyclopropanations with [1.1.1]Propellane

[1.1.1]Propellane is a highly strained tricyclic hydrocarbon whose reactivity is dominated by addition reactions across the central inverted bond to provide bicyclo[1.1.1]pentane derivatives. These reactions proceed under both radical and two-electron pathways, hence, providing access to a diverse array of products. Conversely, transition metal-catalyzed reactions of [1.1.1]propellane are underdeveloped and lack synthetic utility, with reported examples generally yielding mixtures of ring-opened structural isomers, dimers, and trimers, often with poor selectivity. Herein, we report that nickel(0) catalysis enables the use of [1.1.1]propellane as a carbene precursor in cyclopropanations of a range of functionalized alkenes to give methylenespiro[2.3]hexane products. Computational studies provide support for initial formation of a Ni(0)-[1.1.1]propellane complex followed by concerted double C-C bond activation to give the key 3-methylenecyclobutylidene-nickel intermediate.

Methylenespiro[2.3]hexanes via Nickel-Catalyzed Cyclopropanations with [1.1.1]Propellane

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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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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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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

 

Can You Really Do Chemisty Experiments About Vinylferrocene

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Difluoroacetaldehyde N-Triftosylhydrazone (DFHZ-Tfs) as a Bench-Stable Crystalline Diazo Surrogate for Diazoacetaldehyde and Difluorodiazoethane

Despite the growing importance of volatile functionalized diazoalkanes in organic synthesis, their safe generation and utilization remain a formidable challenge because of their difficult handling along with storage and security issues. In this study, we developed a bench-stable difluoroacetaldehyde N-triftosylhydrazone (DFHZ-Tfs) as an operationally safe diazo surrogate that can release in situ two low-molecular-weight diazoalkanes, diazoacetaldehyde (CHOCHN2) or difluorodiazoethane (CF2HCHN2), in a controlled fashion under specific conditions. DFHZ-Tfs has been successfully employed in the Fe-catalyzed cyclopropanation and Doyle?Kirmse reactions, thus highlighting the synthetic utility of DFHZ-Tfs in the efficient construction of molecule frameworks containing CHO or CF2H groups. Moreover, the reaction mechanism for the generation of CHOCHN2 from CF2HCHN2 was elucidated by density functional theory (DFT) calculations.

Difluoroacetaldehyde N-Triftosylhydrazone (DFHZ-Tfs) as a Bench-Stable Crystalline Diazo Surrogate for Diazoacetaldehyde and Difluorodiazoethane

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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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Polymer network formation using the phosphane-ene reaction: A thiol-ene analogue with diverse postpolymerization chemistry

Air-stable primary phosphines were photopolymerized using phosphane-ene chemistry, the phosphorus analogue of the thiol-ene reaction, to fabricate a completely new class of polymer networks. It was demonstrated that the tunable thermal and physical properties accessible using thiol-ene chemistry could also be achieved using an analogous phosphane-ene reaction. At the same time, the presence of the 31P nucleus that is easily observed using NMR spectroscopy allowed the chemical structures of the networks to be directly probed using solid state NMR spectroscopy. Following its incorporation into the network, phosphorus offers the distinct difference and advantage of being able to undergo a diverse array of further derivatization to afford functional materials. For example, the networks were demonstrated to serve as effective oxygen scavengers and to bind transition metals (e.g., Pd). By using the air stable ferrocenyl phosphine (FcCH2CH2)PH2, redox-active networks were produced and these materials could be pyrolyzed to yield magnetic ceramics. Overall, this demonstrates the promise of phosphane-ene chemistry as an alternative to thiol-ene systems for providing functional materials for a diverse range of applications.

Polymer network formation using the phosphane-ene reaction: A thiol-ene analogue with diverse postpolymerization chemistry

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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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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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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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Thermodynamics and kinetics of redox switching of polyvinylferrocene films in perchlorate solutions

Cyclic voltammetry was used to create nonequilibrium populations of different solvation and configurational states of partially oxidized polyvinylferrocene (PVF). Oxidation levels were established by scanning either from a fully reduced state to the desired oxidation level or from a fully oxidized state to the desired level. Coulostatic conditions were then established by opening the external circuit, and subsequent mass and potential changes were followed. The film’s approach to equilibrium involves configurational changes within the polymer and simultaneous and subsequent solvent transfer. At very short times (t a?? 0.2 s) the approach to equilibrium is limited by both solvation and reconfiguration processes. For a short time afterward (0.2 < t/s < 1.0) reconfiguration alone is rate limiting. At intermediate times (1 < t/s < 5) both processes play comparable roles. At long times (r > 5 s) solvation is the controlling step. The electroactive polymer film does not completely reach equilibrium even after 1 h at open circuit as evidenced by continuous small mass changes. These mass changes are the result of water transfer between the polymer film and the bathing electrolyte. A scheme of cubes model rationalizes mechanistic pathways leading to equilibrium. In particular, the observed extrema in mass (solvent population) are predicted. The electrode potential, after 1 h at open circuit, shows nearly Nernstian dependence on the redox composition for film states produced by either anodic or cathodic cyclic voltammetric scans. These Nernst plots are displaced by only a few millivolts because only a weak Nernstian dependence on film water content exists. Films that are 50% oxidized exhibit a sub-Nernstian response with respect to the perchlorate concentration in the bathing solution under permselective conditions.

Thermodynamics and kinetics of redox switching of polyvinylferrocene films in perchlorate solutions

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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