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The atomic bond and molecular polarizabilities of some ferrocene derivatives have been calculated using variational method and delta-function electronic wave functions.Scales have been presented, where the derivatives are classified in order of their polarization properties.Common trends and patterns of behaviour are recognized and discussed.

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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 hybrid CeO2-based biocatalytic nanostructure carrying catalytically active oxygen-rich nanoparticles is described as a general platform for laccase (Lac)-based biocathodes and biofuel cells. To design the bioelectrodes, the particles and the enzyme were deposited on reduced graphene or carbon nanotube-based buckypaper using conducting poly(3,4-ethylenedioxythiophene):polystyrene-sulfonic acid (PEDOT:PSS). The use of CeO2 into the biocatalytic layer enhanced the bioelectrocatalytic reduction current and enabled functionality of the bioelectrode and biofuel cell in oxygen-limited conditions. These results open up new avenues for designing biointerfaces for protecting activity of immobilized enzymes and providing functionality in oxygen-limited environments. The hybrid nanostructure described in this work may be used as a general platform for the immobilization of other enzymes for a variety of biosensing, biofuel cells and bioelectronics applications.

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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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Reactions of Fc?(CHO)2 1 (Fc? = 1,1?-ferrocenediyl) with LiC{triple bond, long}CR gave substituted propargylic alcohols Fc?{CH(OH)C{triple bond, long}CR}2 (R = SiMe3 2, Fc 9). Oxidation (MnO2) of these alcohols afforded the bis(alkynyl ketone)s Fc?{C(O)C{triple bond, long}CR}2 (R = SiMe3 3, Fc 10), the former being accompanied by the partially desilylated Fc?{C(O)C{triple bond, long}CH}-1-{C(O)C{triple bond, long}CSiMe3}-1? 4. The reaction between 4 and RuCl(dppe)Cp in the presence of Na[BPh4] gave the cyclic vinylidene complex [Ru{{double bond, long}C{double bond, long}C[C(O)Fc?C(O)CH{double bond, long}CH]}(dppe)Cp]BPh4 5. The diastereomers were separated by flash chromatography (2) or preparative t.l.c. (9) to give the cis (2a, 9a) and trans (2b, 9b) isomers. Cyclisation of each isomer to the corresponding ferrocenophane was catalysed by pTSA to give Fc?{[CH(C{triple bond, long}CR)]2O} (R = SiMe3 6a, 6b; Fc 11a, 11b), of which 6a, 6b could be desilylated to Fc?{[CH(C{triple bond, long}CH)]2O} 7a, 7b, and further transformed into the bis(eta2-alkyne-dicobalt) complexes Fc?{[CH(eta2-C2H[Co2(mu-dppm)(CO)4])]2O} 8a, 8b with Co2(mu-dppm)(CO)6. Molecular structures of 3, 5, 6a, 6b, 7a, 7b and 10 were determined by single-crystal XRD methods.

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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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The synthesis, electrochemical, electronic, and cation sensing properties of multinuclear nitrogen-rich [2.2]- and [3.3]-mixed ferrocene and ruthenocene metallocenophanes are presented. Structural features of these new structural motifs are that the two redox organometallics fragments are linked by unsaturated nitrogen functionalities, for example, carbodiimide or aldimine, as well as the nitrogen atom is directly attached to the ruthenocene unit. The key bis(iminophosphorane) 3 is readily prepared by the Staudinger reaction between triphenylphosphine and 1,1?-diazidoruthenocene 2, which has been prepared from 1,1?- dilithioruthenocene and 2,4,6-trisopropylbenzenesulfonyl azide (trisyl azide). Subsequent aza-Wittig reactions of 3 with the appropriate carbonyl or thiocarbonyl compounds provided the opened ruthenocenebased isothiocyanate 4, and the closed carbodiimide 5 and aldimines 6 and 7. Spectroelectrochemical studies of carbodiimide 5 and aldimine 7 revealed the presence of low-energy bands in the near-IR region in the partially oxidized forms, at 1029 and 1481 nm, respectively, which indicate the existence of intramolecular charge transfer between the iron and the ruthenium centers. The experimental data and conclusions are supported by DFT computations. Moreover, the aldimine 7 behaves as a selective colorimetric chemosensor molecules for Zn2+ ions. The low-energy (LE) band of the absorption spectrum of this compound is red-shifted by 99 nm, only in the presence of Zn2+ ions. This change in the absorption spectrum is accompanied by a dramatic color change, which allows the potential for “naked eye” detection.

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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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Conditions for the formation of intramolecular hydrogen bonds in alpha-metallocenylcarbinols of the iron subgroup (M = Fe, Ru, Os) are determined.The combination of IR spectral data with conformational calculations has revealed situations where hydrogen bonding with the metal atom is determined by conformational preference.General rules govering the influence of the nature of the metal atom and the effect of substituents in the carbinol group and the cyclopentadienyl rings on the formation constants and relative stability of OH…Me intramolecular hydrogen bonds, on the proton-donating ability of the OH group and on the competition between intra- and intermolecular hydrogen bonds during self-association in the crystal, are estabished.

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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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<3.3>(1,1′)Ruthenocenophane-2,14-diene-1,16-dione, <5.5>(1,1′)ruthenocenophane-2,14,17,29-tetraene-1,16-dione and their ferrocenoruthenocenophane homologs were synthesized by using an intramolecular base-catalyzed condensation.

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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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An efficient and selective new method for the preparation of unsymmetrical 1,1?-disubstituted ferrocenes by a one-pot procedure, starting from ferrocenecarbaldehyde, is disclosed.

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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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Optimized combination of chemical agents was selected for sensitive electrochemical detection of dissolved ruthenium tris-(2,2?-bipyridine) (Ru-bipy). The detection was based on the chemical amplification mechanism, in which the anodic current of a redox-active analyte was amplified by a sacrificial electron donor in solution. On indium-doped tin oxide (ITO) electrodes, electrochemical reaction of the analyte was reversible, but that of the electron donor was greatly suppressed. Several transition metal complexes, such as ferrocene and tris-(2,2?-bipyridine) complexes of osmium, iron and ruthenium, were evaluated as model analyte. A correlation between the amplified current and the standard potential of the complex was observed, and Ru-bipy generated the largest current. A variety of organic bases, acids and zwitterions were assessed as potential electron donor. Sodium oxalate was found to produce the largest amplification factor. With Ru-bipy as the model analyte and oxalate as the electron donor, the analyte concentration curve was linear up to 50muM, with a lower detection limit of approximately 50nM. Preliminary work was presented in which a Ru-bipy derivative was attached to bovine serum albumin and detected electrochemically. Although the combination of Ru-bipy, oxalate and ITO electrode has been used before for electrochemiluminescent detection of Ru-bipy and oxalate, as well as electrochemical detection of oxalate, its utility in amplified voltammetric detection of Ru-bipy as a potential electrochemical label has not been reported previously.

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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 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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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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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