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Formation of functionalized [3]ferrocenophane derivatives by an enamine condensation reaction

Treatment of 1,1?-diacetylferrocene (10) with excess piperidine and a stoichiometric amount of TiCl4 in pentane leads to CC-coupling of the two functional groups at the ferrocene framework. This enamine condensation reaction leads to the formation of the 1,3-connected dienamine-bridged [3]ferrocenophane system 13a. Complex 13a was characterised by X-ray crystal structure analysis. The analogous TiCl4-mediated coupling and condensation reactions of 10 with morpholine, pyrrolidine or methyl-isopropylamine yield the corresponding substituted [3]ferrocenophane systems 13b-d.

Formation of functionalized [3]ferrocenophane derivatives by an enamine condensation reaction

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

 

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Chemistry is an experimental science, and the best way to enjoy it and learn about it is performing experiments. Computed Properties of C14H6FeO2. Introducing a new discovery about 1273-94-5, Name is 1,1′-Diacetylferrocene

Ionic hydrogenation of acylferrocenes using zinc borohydride: An efficient, mild method for the preparation of alkylferrocenes

An effective mild procedure for the reductive deoxygenation of alpha-ferrocenyl aldehydes, ketones, and alcohols into the corresponding alkylferrocenes is described using a combination of zinc borohydride and zinc chloride. This is the first example of such reactivity of zinc borohydride. The present method allows the synthesis of alkylferrocenes bearing terminally functionalized pendant chains.

Ionic hydrogenation of acylferrocenes using zinc borohydride: An efficient, mild method for the preparation of alkylferrocenes

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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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n-Type Molybdenium Diselenide-Based Photoelectrochemical Cells: Evidence for Fermi Level Pinning and Comparison of the Efficiency for Conversion of Light to Electricity with Various Solvent/Halogen/Halide Combinations

Interfacial energetics for n-type MoSe2 (Eg = 1.4 eV, direct) and photoelectrochemical conversion of light to electrical energy in the presence of Xn-/X- (X = Cl, Br, I) have been characterized in CH3CN electrolyte solution.Data for MoSe2 in H2O/I3-/I- are included for comparison, along with a comparison of MoSe2-based cells with MoS2- (Eg = 1.7 eV, direct) based cells.Cyclic voltammetry for a set of reversible (at Pt electrodes) redox couples whose formal potential, <*>, spans a range -0.8 to +1.5 V vs.SCE has been employed to establish the interface energetics of MoSe2.For the redox couples having <*> more negative than ca. -0.1 V vs.SCE, we find reversible electrochemistry in the dark at n-type MoSe2.When <*> is somewhat positive of -0.1 V vs.SCE, we find that oxidation of the reduced form of the redox couple can be effected in an uphill sense by irradiation of the n-type MoSe2 with <*>Eg light; the anodic current peak is at more negative potential than at Pt for such situations.The extent to which the photoanodic current peak is more negative than at Pt is a measure of the output photovoltage for a given couple.For <*> more positive than ca. +0.7 V vs.SCE it would appear that this output photovoltage is constant at ca. 0.4 V.For a redox couple such as biferrocene (<*>(BF+/BF) = +0.3 V vs.SCE) we find a photoanodic current onset at ca. -0.2 V vs.SCE; a redox couple with <*> = 1.5 V vs.SCE shows an output photovoltage of 0.43 V under the same conditions.The ability to observe (i) photoeffects for redox reagents spanning a range of <*>‘s that is greater than the direct Eg and (ii) constant photovoltage for a range of <*>‘s evidences an important role for surface states or carrier inversion such that a constant amount of band bending (constant barrier height) is found for a couple having <*> more positive than ca. +0.7 V vs.SCE.Conversion of <*> light to electricity can be sustained in CH3CN solutions of Xn-/X- (X = Cl, Br, I) with an efficiency that is ordered Cl > Br > I where n-type MoSe2 is used as a stable photoanode.In aqueous solution n-type MoSe2 is not a stable anode in the presence of similar concentrations of Br2/Br- or Cl2/Cl-, showing an important role for solvent in thermodynamics for electrode decomposition.In CH3CN, efficiency for conversion of 632.8-nm light to electricity has been found to be up to 7.5percent for Cl2/Cl-, 1.4percent for Br2/Br-, and 0.14percent for I3-/I-.Differences among these redox systems are output voltage and short-circuit current, accounting for the changes in efficiency.In H2O, I3-/I- yields a stable n-type MoSe2-based photoelectrochemical cell with an efficiency for 632.8-nm light a little lower that for the CH3CN/Cl2/Cl- solvent/redox couple system.Data for MoS2-based cells in the CH3CN/Xn-/X- solvent/redox couple systems show that the efficiency again depends on X: Cl > Br >I. …

n-Type Molybdenium Diselenide-Based Photoelectrochemical Cells: Evidence for Fermi Level Pinning and Comparison of the Efficiency for Conversion of Light to Electricity with Various Solvent/Halogen/Halide Combinations

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

 

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Unexpected formation of novel benzofuranyl-substituted ferrocenes by action of p-benzoquinone on 1,1′-bis-acylferrocene

A Michael addition was found to occur between 1,1′-bis-(undecanoyl)ferrocene and p-benzoquinone in the presence of tetrafluoroboric acid leading to the formation of benzofuranyl ferrocene derivatives.Under similar conditions, the fluoroalkyl 1,1′-bis<11-(F-octyl)-undecanoyl>ferrocene and the acetylferrocene analogue are oxidized to their respective ferricinium ions.

Unexpected formation of novel benzofuranyl-substituted ferrocenes by action of p-benzoquinone on 1,1′-bis-acylferrocene

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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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Synthesis of new ferrocene derivatives with a 4,5-dichloroisothiazole fragment

Conjugates of ferrocene and 4,5-dichloroisothiazole were synthesized, where the ferrocene and isothiazole moieties are linked through various structural fragments. The acylation of ferrocene with 4,5- dichloroisothiazole-3-carbonyl chloride gave (4,5-dichloroisothiazol-3-yl) ferrocenyl ketone; the acylation of aminomethylferrocene furnished the corresponding amide. The esterification of ferrocene-1,1?-dicarboxylic acid with 4,5-dichloroisothiazol-3-yl-methanol resulted in the formation of the corresponding ester. The condensation of 1,1?-diacetylferrocene with 4,5-dichloroisothiazole-3-carbaldehyde afforded ferrocenophane containing 4,5-dichloroisothiazole moieties.

Synthesis of new ferrocene derivatives with a 4,5-dichloroisothiazole fragment

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Conformation-switched chemosensor for selective detection of Hg2+ in aqueous media

A conformation flexible chemosensor for selective detection of Hg2+ in aqueous media was achieved by incorporating two well-known rhodamine-6G dyes and a ferrocene group within one molecule. Distinguished from the monosubstituted ferrocene derivative which is previously reported a lack of interaction with Hg2+, the title compound was characteristic of two-armed bidendate binding unit. The Hg2+ sensing behavior can be switched via the conformation flexibility. The 1:1 sensor/Hg2+ binding mode was proposed and supported by the titration experiment and ESI mass spectrum. The fluorescent sensor can display a highly selective response of fluorescence enhancement toward Hg2+ and detect the parts per billion (ppb) level of Hg2+ in aqueous environment. Crown Copyright

Conformation-switched chemosensor for selective detection of Hg2+ in aqueous media

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Substituent effects on ferrocenes in aluminum chloride-butylpyridinium chloride molten-salt mixtures

The visible absorption spectra and reduction potentials of 11 ferrocenes containing electron-withdrawing substituents were determined in an N-n-butylpyridinium chloride-aluminum chloride molten salt. When the substituent(s) on the cyclopentadienyl ring(s) of ferrocene were varied, the reduction potential was caused to range over 1.25 V, and the wavelength for maximum absorption of visible light was varied by nearly 200 nm. These changes are greater than have been observed for similar ferrocenes in other nonaqueous solvents. Evidence is presented for specific interactions of particular ferrocenes with the molten salt.

Substituent effects on ferrocenes in aluminum chloride-butylpyridinium chloride molten-salt mixtures

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

 

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Study on ferrocene derivatives diffusion dynamics in polymer electrolyte by solid-state voltammetry

The diffusion rates of seven ferrocene derivatives have been estimated in polyelectrolyte PEG ¡¤ LiClO4 by using non-steady-state chronoamperometry. The Dapp of ferrocene derivatives increases with temperature, and the dependency of Dapp on temperature obeys the Arrhenius equation. The Dapp of ferrocene derivatives decreases with increasing size of electroactive species. The DeltaDapp values of DT>Tm and DT Tm in the polyelectrolyte. On the other hand, the diffusion behaviour of ferrocene derivatives is qualitatively analyzed by using cyclic voltammetry. Copyright

Study on ferrocene derivatives diffusion dynamics in polymer electrolyte by solid-state voltammetry

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Metal-metal charge transfer and solvatochromism in cyanomanganese carbonyl complexes of ruthenium and osmium

The complexes [(H3N)5RuII(-NC)Mn ILx]2+, prepared from [Ru(OH 2)(NH3)5]2+ and [Mn(CN)L x] {Lx = trans-(CO)2{P(OPh)3}(dppm); cis-(CO)2(PR3)(dppm), R = OEt or OPh; (PR 3)(NO)(eta-C5H4Me), R = Ph or OPh}, undergo two sequential one-electron oxidations, the first at the ruthenium centre to give [(H3N)5RuIII(-NC)MnIL x]3+; the osmium(iii) analogues [(H3N) 5OsIII(-NC)MnILx]3+ were prepared directly from [Os(NH3)5(O3SCF 3)]2+ and [Mn(CN)Lx]. Cyclic voltammetry and electronic spectroscopy show that the strong solvatochromism of the trications depends on the hydrogen-bond accepting properties of the solvent. Extensive hydrogen bonding is also observed in the crystal structures of [(H 3N)5RuIII(-NC)MnI(PPh 3)(NO)(eta-C5H4Me)][PF6] 3¡¤2Me2CO¡¤1.5Et2O, [(H 3N)5RuIII(-NC)MnI(CO)(dppm) 2-trans][PF6]3¡¤5Me2CO and [(H3N)5RuIII(-NC)MnI(CO) 2{P(OEt)3}(dppm)-trans][PF6] 3¡¤4Me2CO, between the ammine groups (the H-bond donors) at the Ru(iii) site and the oxygen atoms of solvent molecules or the fluorine atoms of the [PF6]- counterions (the H-bond acceptors). The Royal Society of Chemistry 2006.

Metal-metal charge transfer and solvatochromism in cyanomanganese carbonyl complexes of ruthenium and osmium

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Development of [3]ferrocenophane-derived N/B frustrated Lewis pairs for the metal-free catalytic hydrogenation of imines

A series of novel [3]ferrocenophane-derived N/B frustrated Lewis pairs (FLPs) were synthesized and successfully applied to the catalytic hydrogenation of imines in 71?93% yields. This approach could be easily conducted on gram scale and provided versatile synthetic route for the key intermediate of sertraline hydrochloride without heavy metal residues.

Development of [3]ferrocenophane-derived N/B frustrated Lewis pairs for the metal-free catalytic hydrogenation of imines

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