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Solvent Dynamical Effects in Electron Transfer: Evaluation of Electronic Matrix Coupling Elements for Metallocene Self-Exchange Reactions

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.

Solvent Dynamical Effects in Electron Transfer: Evaluation of Electronic Matrix Coupling Elements for Metallocene Self-Exchange Reactions

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A double-helix generated from a ferrocenyl-thiosemicarbazato metallo-synthon and its novel hydrogen-bonding cavities

A double helical architecture generated from a readily prepared ferrocenyl-containing bisthiosemicarbazone ligand is described together with its application to the self-assembly of novel supramolecular hydrogen-bonding cavities.

A double-helix generated from a ferrocenyl-thiosemicarbazato metallo-synthon and its novel hydrogen-bonding cavities

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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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Parylene C coated microelectrodes for scanning electrochemical microscopy

Herein, we present a simple microelectrode preparation methodology consisting in coating a platinum wire or a carbon fiber with a thin insulating Parylene C film (e.g. 1-10 mum), to produce SECM probes with a small and constant probe RG (i.e. ratio between the radius of the insulating sheath and the radius of the active electrode area). After exposition of a fresh active electrode area by blade cutting, a disc shaped electrode is obtained thanks to a protective hot mounting wax layer that avoids Parylene C coating deformation and is easily removed with acetone. Stiffness and straightness of the probe can be tuned by modifying the Parylene C coating thickness and the length of the carbon fiber or platinum wire. This simple electrode preparation method is highly reproducible (c.a. > 90%). The prepared Parylene C coated microelectrodes were characterized by optical microscopy, cyclic voltammetry, scanning electrochemical microscopy (SECM) approach curves and finally applied to SECM imaging of Pt band structures in contact-less and contact mode.

Parylene C coated microelectrodes for scanning electrochemical microscopy

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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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Synthesis of N?-substituted derivatives of 5-(4-methylphenyl)isoxazole-3-carbohydrazonamide

Condensation of aromatic, isoxazole, and ferrocene aldehydes as well as 1,1?-diacetylferrocene with 5-(4-methylphenyl)isoxazole-3-carbohydrazonamide afforded various N-substituted azines with molecular fragments of the corresponding aldehydes or diacetylferrocene.

Synthesis of N?-substituted derivatives of 5-(4-methylphenyl)isoxazole-3-carbohydrazonamide

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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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Preparation of mannitol-based ketal-linked porous organic polymers and their application for selective capture of carbon dioxide

Four kinds of mannitol-based ketal-linked porous organic polymers (MKPOPs) were successfully synthesized through condensation reaction between aromatic acetyl monomers and mannitol, catalyzed by p-toluenesulfonic acid. The structure of resulting polymers was confirmed by Fourier transform infrared and solid-state 13C nuclear magnetic resonance spectrum measurements. The porosities of MKPOPs were investigated by gas adsorption experiments and the results indicate high carbon dioxide uptake (up to 11.5 wt% at 273 K and 1.0 bar) for MKPOPs due to the predominant microporous and hydroxyl-rich structures. Remarkably, MKPOPs exhibit excellent selective adsorption performances for carbon dioxide over methane (9.9-14.2, IAST at 273 K and 1.0 bar). These studies are of significant importance for MKPOPs and their potential application in selective gas adsorption.

Preparation of mannitol-based ketal-linked porous organic polymers and their application for selective capture of carbon dioxide

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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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Carbon Nanotube Immobilized Electrode Using Amphiphilic Phospholipid Polymer with Anti-fouling and Dispersion Property for Electrochemical Analysis

A carbon nanotube (CNT)-modified electrode was fabricated by dropping a dispersion of multi-walled CNTs in water-soluble and amphiphilic phospholipid polymer with both dispersing ability and anti-biofouling property onto a Au electrode. A poly(2-methacryloyloxyethyl phosphorylcholine-co-n-butyl methacrylate) (PMB) composed from 50 mol% of 2-methacryloxylethyl phosphorylcholine and 50 mol% of n-butyl methacrylate (PMB50) was used as dispersing reagent for CNTs. The dispersion of water-insoluble material by PMB50 and its antifouling effects in electrochemical analysis were investigated. The CNT-modified electrode showed an anodic peak potential that was shifted negatively and an increase in the current value for the electrolytic oxidation of nicotinamide adenine dinucleotide. In addition, the charge on PMB50 did not inhibit the electrochemical reaction of the redox compounds K3[Fe(CN)6], [Ru(NH3)6]Cl3, and hydroxymethylferrocene. Cyclic voltammetry of K3[Fe(CN)6] in 4 % bovine serum albumin (BSA) using a bare Au electrode, the anodic peak current was reduced to 47 % of that without BSA. In contrast, the antifouling effect of the PMB50-coated electrode meant that the current was only reduced to 70 % of that without BSA.

Carbon Nanotube Immobilized Electrode Using Amphiphilic Phospholipid Polymer with Anti-fouling and Dispersion Property for Electrochemical Analysis

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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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Redox mediation at 11-mercaptoundecanoic acid self-assembled monolayers on gold

Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and digital simulation techniques were used to investigate quantitatively the mechanism of electron transfer (ET) through densely packed and well-ordered self-assembled monolayers (SAMs) of 11-mercaptoundecanoic acid on gold, either pristine or modified by physically adsorbed glucose oxidase (GOx). In the presence of ferrocenylmethanol (FcMeOH) as a redox mediator, ET kinetics involving either solution-phase hydrophilic redox probes such as [Fe(CN) 6]3-/4- or surface-immobilized GOx is greatly accelerated: [Fe(CN)6]3-/4- undergoes diffusion-controlled ET, while the enzymatic electrochemical conversion of glucose to gluconolactone is efficiently sustained by FcMeOH. Analysis of the results, also including the digital simulation of CV and EIS data, showed the prevalence of an ET mechanism according to the so-called membrane model that comprises the permeation of the redox mediator within the SAM and the intermolecular ET to the redox probe located outside the monolayer. The analysis of the catalytic current generated at the GOx/SAM electrode in the presence of glucose and FcMeOH allowed the high surface protein coverage suggested by X-ray photoelectron spectroscopy (XPS) measurements to be confirmed.

Redox mediation at 11-mercaptoundecanoic acid self-assembled monolayers on gold

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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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A DFT-Elucidated comparison of the solution-phase and SAM electrochemical properties of short-chain mercaptoalkylferrocenes: Synthetic and spectroscopic aspects, and the structure of Fc- CH2CH2-S-S-CH2CH2-Fc

Facile synthetic procedures to synthesize a series of difficult-To-obtain mercaptoalkylferrocenes, namely, Fc(CH2)nSH, where n = 1 (1), 2 (2), 3 (3), or 4 (4) and Fc = Fe(n5-C5H5)(n5-C5H4), are reported. Dimerization of 1-4 to the corresponding disulfides 19-22 was observed in air. Dimer 20 (Z = 2) crystallized in the triclinic space group Pi. Dimers 20-22 could be reduced back to the original Fc(CH2)nSH derivatives with LiAlH4 in refluxing tetrahydrofuran. Density functional theory (DFT) calculations showed that the highest occupied molecular orbital of 1-4 lies exclusively on the ferrocenyl group implying that the electrochemical oxidation observed at ca. -15 < Epa < 76 mV versus FcH/FcH+ involves exclusively an Fe(II) to Fe(III) process. Further DFT calculations showed this one-electron oxidation is followed by proton loss on the thiol group to generate a radical, Fc(CH2)nS, with spin density mainly located on the sulfur. Rapid exothermic dimerization leads to the observed dimers, Fc(CH2)n-S-S- (CH 2)nFc. Reduction of the ferrocenium groups on the dimer occurs at potentials that still showed the ferrocenyl group E = Epa,monomer - Epc,dimer ? 78 mV, indicating that the redox properties of the ferrocenyl group on the mercaptans are very similar to those of the dimer. 1H NMR measurements showed that, like ferrocenyl oxidation, the resonance position of the sulfhydryl proton, SH, and others, are dependent on -(CH2)n- chain length. Self-Assembled monolayers (SAMs) on gold were generated to investigate the electrochemical behavior of 1-4 in the absence of diffusion. Under these conditions, deltaE approached 0 mV for the longer chain derivatives at slow scan rates. The surface-bound ferrocenyl group of the metal-Thioether, Fc(CH)n -S-Au, is oxidized at approximately equal potentials as the equivalent CH2Cl2-dissolved ferrocenyl species 1-4. Surface coverage by the SAMs is dependent on alkyl chain length with the largest coverage obtained for 4, while the rate of heterogeneous electron transfer between SAM substrate and electrode was the fastest for the shortest chain derivative, Fc-CH2-S-Au. A DFT-Elucidated comparison of the solution-phase and SAM electrochemical properties of short-chain mercaptoalkylferrocenes: Synthetic and spectroscopic aspects, and the structure of Fc- CH2CH2-S-S-CH2CH2-Fc Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.Electric Literature of 1273-86-5. In my other articles, you can also check out more blogs about 1273-86-5

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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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In heterogeneous catalysis, the catalyst is in a different phase from the reactants. Application In Synthesis of 1,1′-Diacetylferrocene, At least one of the reactants interacts with the solid surface in a physical process called adsorption in such a way. 1273-94-5, name is 1,1′-Diacetylferrocene. In an article£¬Which mentioned a new discovery about 1273-94-5

Synthesis of alpha-arylalkylferrocenes through cesium fluoride-promoted coupling of arylboronic acids with N-tosylhydrazones

A cesium fluoride-promoted reductive coupling reaction of acylferrocene tosylhydrazones with arylboronic acids has been developed, producing highly substituted alpha-arylalkylferrocenes in moderate to excellent yields. The reaction employs anionic fluorine to facilitate the cleavage of C?B bond. The developed methodology demonstrates a wide substrate scope and high functional groups tolerance. Moreover, the alpha-arylalkylferrocenes compounds were also obtained on a multi-gram scale.

Synthesis of alpha-arylalkylferrocenes through cesium fluoride-promoted coupling of arylboronic acids with N-tosylhydrazones

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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 and electronic properties of ferrocene-containing organic dyads

Novel ferrocene-oligothiophenylene-cyanoacrylic acid in the form of donor-spacer-acceptor dyads was synthesized. The compound with a single unit of thiophenylene showed the lowest energy transition in neutral state. For radical cations, the lowest energy transition appears red-shifted along with the increased number of thiophenylene units. These results suggested that the electronic structure of radical cations is significantly different from that of neutral molecules.

Synthesis and electronic properties of ferrocene-containing organic 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