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This work presents an electrochemical study of enhanced electronic communication based on intermolecular hydrogen-bonding in ferrocenemethanol (described as FcCH2OH) molecular clusters. The enhanced electronic communication in FcCH2OH clusters is confirmed and further investigated by differential-pulse voltammetry and cyclic voltammetry. A key finding is that this enhanced electronic communication increases the standard rate constant of the electron transfer process. These results will provide us with a further understanding of the electronic communication within the ferrocenyl derivatives which is based on the intermolecular hydrogen-bonding.

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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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The iron(III) protoporphyrin IX complex with imidazole, a biologically relevant ligand, occupying an axial position, has been studied by infrared multiple photon dissociation (IRMPD) spectroscopy. The complex has been delivered in gas-phase by electrospray ionization (ESI), mass selected in an ion trap, and assayed by IRMPD spectroscopy in two complementary frequency regions. The fingerprint range (900-1900 cm-1) has been scanned using the Orsay free-electron laser beamline (CLIO), while the X-H (X = C,N,O) stretching region (3000-3600 cm-1) has been inspected using a tabletop IR optical parametric oscillator/amplifier (OPO/OPA) laser source. DFT calculations have been performed to obtain a comprehensive pattern of the various potential conformers yielding optimized geometries, relative thermodynamic parameters, and respective IR spectra. The comparison between the IR spectra for representative conformers and the experimental IRMPD features suggests the coexistence of two families of conformers involving different degrees of folding and hydrogen bonding between the two propionic acid functionalities on the periphery of the protoporphyrin IX macrocycle in a ratio depending on environmental conditions such as ESI solvent and temperature. The observed conformational variability of the porphyrin substituents in the naked heme-imidazole complex is consistent with the fine-tuning of the reactivity properties of this important prosthetic group by the specific surroundings in the protein core.

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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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As a society publisher, everything we do is to support the scientific community – so you can trust us to always act in your best interests, Synthetic Route of 1273-94-5, and get your work the international recognition that it deserves. Introducing a new discovery about 1273-94-5, Name is 1,1′-Diacetylferrocene

1,1?-Bis(1,1-dimethylsulfanyl-3-oxo-1-propene)ferrocene and 1,1?-Bis(methyl-3-hydroxy-prop-2-ene-dithioate)ferrocene have been shown to be useful three-carbon synthons for the efficient synthesis of hitherto unreported and synthetically demanding Fc-heterocycles. Five-membered (pyrazole, isoxazole, and thiophene) and six-membered (pyrimidine, coumarin, and quinoline) heterocycles have been constructed on both Cp rings of the ferrocene matrix via regioselective heteroaromatic annulation. The Royal Society of Chemistry.

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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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This paper describes the synthesis of a new class of [N,P] ligands based on pyrrole with a dimethylamino group as hard donor and a phosphine moiety as soft base. We have also modified the phosphine fragment to change the electronic and steric properties of these ligands. Palladium complex 3a proved to be very efficient in Heck cross-coupling reactions and in intramolecular aryl-aryl couplings of esters and amides. We have demonstrated the applicability and efficiency of this novel catalyst in the total synthesis of the natural product arnottin I.

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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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The diruthenium(II,II) complex [Ru2(L1)(OAc)3]Cl (1), spanned by a naphthyridine-diimine ligand and bridged by three acetates, has been synthesized. The catalytic efficacy of complex 1 has been evaluated for the acceptorless dehydrogenation (AD) of alcohols and for the dehydrogenative coupling reactions of alcohols with Wittig reagents. The diruthenium(II,II) complex is an excellent catalyst for AD of a diverse range of alcohols, and it is shown to be particularly effective for the conversion of primary alcohols to the corresponding aldehydes without undesired side products such as esters. Triphenylphosphonium ylides in a one-pot reaction with alcohols afforded the corresponding olefins in high yields with excellent E selectivity. The liberated dihydrogen gas was identified and measured to be 1 equiv with respect to alcohol. Deuteration studies with PhCD2OH revealed the absence of isotope scrambling in the product, indicating the involvement of a Ru-monohydride intermediate. Kinetic studies and DFT calculations suggest a low-energy bimetallic beta-hydride elimination pathway where rate-limiting intramolecular proton transfer from alcohol to metal-bound hydride constitutes the dehydrogenation step. The general utility of metal-metal bonded compounds for alcohol AD and subsequent coupling reactions is demonstrated here.

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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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A new form of high surface bioelectrode based on electrospun gold microfiber with-immobilized glucose oxidase was developed. The gold fibers were prepared by electroless deposition of gold nanoparticles on a poly(acrylonitrile)-HAuCl4 electrospun fiber. The material was characterized using electron microscopy, XRD and BET, as well as cyclic voltammetry and biochemical assay of the immobilized enzyme. The surface area of the gold microfibers was 2.5 m2/g. Glucose oxidase was covalently crosslinked to the gold surface using cystamine monolayer and glutardialdehyde, and portrayed characteristic catalytic currents for oxidizing glucose using a ferrocene methanol mediator. Limit of detection of glucose is 0.1 mM. The K m of the immobilized enzyme is 10 mM, in accordance with other reports of immobilized glucose oxidase. The microfiber electrode was reproducible and showed correlation between fiber weight, cathodic current and enzymatic loading.

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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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Cellulose nano-whiskers or nanocrystals are used as a carbon source in a vacuum graphitisation process to surface-modify nano-TiO2 and influence its photoreactivity. In sharp contrast to bulk carbon-modified TiO2 materials, introducing cellulose in a controlled way, i.e., a layer-by-layer deposition process, allows thin film materials to be created with low graphite content, but with strongly suppressed responses to light. The effect is explained by highly effective surface recombination and demonstrated for the I3-/I- redox system in acetonitrile and for the photo-oxidation of acetate in aqueous media.

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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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Coordinative directed assembly has been used by a number of research groups to obtain molecular squares featuring porphyrin components. The syntheses and functional behavior of these compounds are reviewed.

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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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A functional group exchange reaction between allylamines and alkenes via nickel-catalyzed C – C bond cleavage and formation was developed. This reaction provides a novel protocol, which does not require the use of unstable imine substrates, for the synthesis of allylamines, which are widely used in the production of fine chemicals, pharmaceuticals, and agrochemicals.

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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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The functional dependence of the rate constants for self-exchange, kex, for a series of metallocene redox couples to solvent-induced variations in the nuclear frequency factor, nun, engendered by alterations in the longitudinal solvent relaxation time, tauL, are utilized to deduce values of the electronic matrix coupling element, H12, for electron exchange.The analysis exploits the sensitivity of the kex-tauL-1 dependence to the degree of reaction adiabaticity and hence H12 for a given electron-exchange reaction.Six metallocene couples are examined:Cp2Co+/0, Cp2Fe+/0 (Cp = cyclopentadienyl), the decamethyl derivatives Cp’2Co+/0 and Cp’2Fe+/0 scrutinized previously, with additional solvent-dependent kex values for (carboxymethyl)cobaltocenium-(carboxymethyl)cobaltocene and (hydroxymethyl)ferrocenium-(hydroxymethyl)ferrocene .Kinetic data are examined in 15 solvents, including 11 “Debye” solvents for which it is anticipated that nun <*> tauL-1.Corrections to kex for the solvent-dependent variations in the barrier height were obtained by corresponding measurements of the optical electron-transfer energies for the related binuclear complex biferrocenylacetylene, yielding “barrier-corrected” rate constants, k’ex.The k’ex-tauL-1 dependencies, as well as the kex values in a given solvent, are markedly dependent on the redox couple.The log k’ex-log tauL-1 plots for the most facile couple, Cp’2Co+/0, exhibit slopes approaching unity for smaller tauL-1 values.The less facile couples yield smaller slopes, diminishing in the same sequence that k’ex decreases in a given solvent: Cp’2Co+/0 >Cpe2Co+/0 > Cp2Co+/0 >/= Cp’2Fe+/0 > Cp2Fe+/0 >/= HMFc+/0.These findings are consistent with H12 decreasing in the same order.Comparison of such rate-solvent friction dependencies with corresponding plots calculated using a combined solvent friction-electron tunneling model yields the following approximate values of the matrix coupling element for reactant “closest approach”, H012 (kcal mol-1): Cp’2Co+/0, 1.0; Cpe2Co+/0, 0.5-1.0; Cp2Co+/0, 0.5; Cp’2Fe+/0, 0.2; Cp2Fe+/0, 0.1; HMFc+/0, 0.075.Reasonable concordance is seen with recent theoretical estimates of H012 for Cp2Co+/0 and Cp2Fe+/0.The relationship between H012 and metallocene electronic structure is briefly discussed.The analysis also enables effective solvent relaxation times for adiabatic barrier crossing in non-Debye media, including primary alcohols, to be extracted.

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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