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A combination of electrochemical and radiotracer methods offers a unique possibility of studying the motion of counter- and co-ions during electrochemical transformations occurring in a polymer film. In addition, information can be obtained about the embedding of electrolytes during electropolymerization penetration of electrolytes into the films prepared by solvent-evaporation procedures, the ion-exchange behavior, and the mechanism of the redox processes. Results on poly/vinyl ferrocene/tetracyanoquinodimethane polyester, polypyrrole, and polyaniline are described.

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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 general bioanalytical platform for biosensor applications was developed based on three-dimensional ordered macroporous (3DOM) gold film modified electrodes using lactate oxidase (LOx) as a case study, within the framework of developing approaches of broad applicability. The electrode was electrochemically fabricated with an inverted opal template, making the surface area of the 3DOM gold electrode up to 18 times higher than that of bare flat gold electrodes. These new electrochemical transducers were characterized by using Field Emission Scanning Electron Microscopy (FE-SEM), Atomic Force Microscopy (AFM) and the X-ray diffraction (XRD). The biosensor was developed by immobilization of lactate oxidase (LOx), on a 3DOM gold electrode modified with a self-assembled monolayer of dithiobis-N-succinimidyl propionate (DTSP). The resulting lactate oxidase biosensor was characterized by electrochemical impedance spectroscopy (EIS). The 3DOM gold electrode not only provides a good biocompatible microenvironment but also promotes the increase of conductivity and stability. Thus, the developed lactate oxidase bioanalytical platforms showed higher mediated bioelectrocatalytic activity compared to others previously described based on polycrystalline gold transducers. The response to varying lactate concentrations has been obtained in the presence of hydroxymethylferrocene as redox mediator in solution. Under these conditions, the bioanalytical platform response for DTSP covalently bound enzyme was improved with respect to that obtained in absence of DTSP.

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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 variety of alkenylcarbene complexes [Cp'(CO)2Mn= C(OEt)CH=CHR] (3) (Cp’ = TiS-MeCsH4) was obtained in a straightforward manner upon aldol condensation of [Cp'(CO)2Mn=C(OEt)CH3] (1) with aromatic and alpha,beta- unsaturated aldehydes RC(H)O (2). The reaction is totally stereoselective, giving (E)- or (all-E)-alkenylcarbenes only. The protonation of 3 at low temperature followed by reaction with water affords the alpha,beta-unsaturated aldehyde complexes [Cp'(CO)2Mn(n2-RCH=CHCHO] (5), from which the aldehydes RC(H)=C(H)C(H)O (6) were displaced by acetonitrile. The intermediate aldehyde complexes are shown to result from the hydrolysis of a transient cationic pi- allyl species [Cp'(CO)2Mn(n3-RCHCHC(OEt)H]+ ([4]+) formed upon protonation of 3.

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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 catalytic asymmetric construction of silicon-stereogenic silanes is of great interest and significance, but has met with only limited success to date. We herein report the enantioselective hydrosilylation of alkenes with dihydrosilanes by a chiral half-sandwich scandium catalyst, which constitutes an efficient and general route for the synthesis of a wide range of enantioenriched silicon-stereogenic silanes from easily accessible starting materials. This reaction features a broad substrate scope, high yields, and high enantioselectivity. Some of the chiral tertiary silane products were also converted into valuable derivatives, such as chiral silanol, quaternary silane, and benzosilole compounds.

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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 series of ferrocenyl ended dendrons containing pi-conjugated systems were obtained using Wittig and Heck reactions. The dendrons were attached to eight functionalized resorcinarenes via Williamson reaction obtaining high molecular weight dendrimers. No electronic communication between metal centers was observed by cyclic voltammetry. All the dendrimers were characterized by 1H, 13C NMR, FTIR, UV-Vis, MALDI-TOF, elemental analyses, and electrochemical studies.

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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

 

Something interesting about Ferrocenemethanol

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A novel photoelectrochemical cell consisting of a set of organic thin films which generate photocurrents in opposite directions was fabricated. The polythiophene film containing 5,10,15,20-tetraphenylporphyrin (TPP) and fullerene (C60) generated anodic photocurrents in the presence of ferrocene, while that containing TPP alone generated cathodic photocurrents under aerobic condition. The combination of these two film-modified electrodes showed a better cell performance than the simple sum of these two independent photoelectrochemical cells. A push-pull type, double-driven photoelectrochemical cell is proposed in this paper.

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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 chapter summarizes research work showing that electrostatic interactions may have considerable effects on the stability of complexes formed by the cucurbit[n]uril hosts. Focusing primarily on work carried out by the author’s research group with the cucurbit[7]uril (CB[7]) molecular receptor, this review highlights the role played by electrostatic interactions involving the host cavity portals, in which considerable negative charge density accumulates due to the carbonyl oxygens lacing the portal rims. Electrostatics are responsible for diminished binding affinities between CB[7] and a number of anionic guests containing one or more carboxylate groups. These electrostatic interactions can be used effectively to control the average location of CB[7] along axle-type guests having terminal -COOH groups as a function of their state of protonation, leading to switchable pseudorotaxane systems. They can also be utilized to advantage to develop favorable lateral interactions between CB[7] and other molecular receptors, which results in systems showing cooperative self-assembly.

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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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Reductive amination of ferrocenecarbaldehyde with several primary and secondary amines in the presence of sodium triacetoxyborohydride was studied. This method was used for the synthesis of new ferrocenylmethylamines, viz., N-(ferrocenylmethyl)isoleucine methyl ester, N,N-bis(ferrocenylmethyl)glycine ethyl ester, and N-(3,5-dibenzyloxybenzyl)-N-(ferrocenylmethyl)methylamine. The latter is a potential precursor of a dendrimer with the chiral ferrocenyl plane in the 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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Compounds of the formula I in the form of enantiomerically pure diastereomers or a mixture of diastereomers, (I), where the radicals R1 are identical or different and are each C1-C4-alkyl; m is 0 or an integer from 1 to 3; n is 0 or an integer from 1 to 4; R2 is a hydrocarbon radical or a C-bonded heterohydrocarbon radical; Cp is unsubstituted or C1-C4-alkyl-substituted cyclopentadienyl; Y is a C-bonded chiral group which directs metals of metallation reagents into the ortho position; and Phos is a P-bonded P(III) substituent. The compounds are chiral ligands for complexes of transition metals which are used as homogeneous catalysts in asymmetric syntheses.

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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 method was introduced to research the corrosion resistance of enamel coatings which were sintered at different temperatures in this paper.1-4 Scanning electrochemical microscopy (SECM) conjunction with capacitance-potential test and Mott-Schottky analysis technique were used to study the coating failure process and semiconductor conduction behavior of enamel coating in 3.5wt.% NaCl solution. The high strength steel (SAPH440) was selected as the metal substrate. The coatings which were sintered at different temperatures on the high strength steel were analyzed and their corrosion behaviors and microstructures were also measured by potentiodynamic polarization curves, Mott-Schottky analysis technique and scanning electrochemical microscopy.5-10 In this paper, five kinds of enamel coatings were prepared on high strength steel. The SECM results show that the Faraday current of the microprobe tip gradually decreases with the soaking time increasing, which indicates that the coatings become failure slowly with the invasion of water and aggressive ions. At the same time, the tip current was homogeneous during the immersion process, which reflected that the surface of the sample remained stable, no obvious bulges appeared. Capacitance-potential test and Mott-Schottky analysis7,8 show that the external ions and water molecules gradually penetrate into the coating; coating showed characteristics of n-type semiconductor as time increases, the capacitance increases gradually, the space charge layer thickness decreases, slope of Mott-Schottky curve decreased gradually which indicates that the failure of coating in the process of soaking slowly with the charge carrier density increases.

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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