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The redox behavior and kinetic parameters of five ferrocene derivatives were investigated in 1M LiPF6 in 50:50 volume percent EC:EMC, a typical electrolyte used in lithium-ion batteries. Using cyclic voltammetry (CV) and rotating disk electrode voltammetry (RDE) techniques, the effect of electron donating and withdrawing substituents on each derivative was evaluated from the view point of the Hammett substituent constant. We found that electrochemical rate constants of the ferrocene derivatives can be related to the Hammett equation which gives an accurate approximation for predicting the oxidation potential of redox shuttles when changes are desired in their electron donating and electron withdrawing properties by means of functional group substitution. Our results show that the exchange current density and reaction rate for oxidation decrease as the electron withdrawing property of the substituent increases. It is also shown that electron donating and electron withdrawing property of a substituent affect the exchange current density and electrochemical oxidation reaction rate obeying a trend opposite to that of the Hammett substituent constants (sigma). The correlations found here are expected to improve the ability to systematically design chemical overcharge protection reagents through judicious substitution of functional groups on redox shuttles.

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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 soluble (E)-poly(p-phenylenephosphaalkene) having sterically encumbering ligands has been prepared by a phospha-Wittig reaction. This material exhibits a bathochromic shift with respect to E-PPV and with respect to representative model oligomers. We also report the first fluorescence study of a poly(p-phenylenephosphaalkene) and find that this material exhibits fluorescence, though with modest intensity relative to similarly sized carbon-based analogues.

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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 deoxygenation of acylferrocenes to the corresponding alkylferrocenes proceeded in excellent yields on utilizing a combination of sodium cyanotrihydroborate and boron trifluoride-diethyl ether.This method allows the synthesis of alkylferrocenes with functionalized tethers and is adaptable to large-scale preparations.

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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 invention provides monoferrocenyl compounds of general formula (I). The invention also provides substrates labelled with the compounds, functionalised derivatives of the compounds and methods of using the compounds, functionalised derivatives and labelled substrates in electrochemical assays.

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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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Treatment of the a-dimethylamino[3]ferrocenophane derivative 3 with n-butyllithium results in a directed o-metalation at the adjacent Cp ring of the ferrocene unit to selectively yield the (R*,R*,p-S*) diastereomer 4. Similarly, lithiation of rac-12 gives (R*,p-S*)-13. Both these compounds form mesc-type dimers in the crystal that feature a central C2Li2 four-membered-ring moiety. Compound 13 crystallizes with excess n-butyllithium to form a (13-n-BuLi) dimer that was also characterized by X-ray diffraction. Directed lithiation of the nonbridged ferrocene derivative l-(dimethylaminobenzyl)ferrocene (16) with tertbutyllithium resulted in an opposite stereoselectivity to yield (R*,p-R*)-17, which forms a chiral dimeric structure in the solid state, as was revealed by its X-ray crystal structure analysis.

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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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Reactive oxygen species (ROS) are vital metabolites in numerous biological functions. Disorders of cellular mechanisms can cause overproduction of ROS and, subsequently, oxidative damage to DNA, proteins, cells and tissues, which is associated with the pathogenesis of a number of neurodegenerative and inflammatory diseases. Development of highly sensitive, relatively simple and fast-to-implement innovative methods to detect oxidative stress requires understanding of how such disorders relate to the level of ROS. This research aimed to apply the biological fluids’ ROS detection method we have developed (using the stable platinum nanoelectrode that allows assessing the level of hydrogen peroxide (H2O2) down to 1 muM) and determine the level of H2O2 in lacrimal and intraocular fluids of rabbits, as well as to investigate how the level of H2O2 changes under the influence of antioxidant therapy. The effect superoxide dismutase (SOD) nanoparticles produce on biological fluids’ ROS level was shown. The level of H2O2 in lacrimal fluid increased 10 and 30 min after instillation of SOD nanoparticles. As for the intraocular fluid, H2O2 concentration starts to grow only 30 min after instillation of SOD nanoparticles, which suggests that the they penetrate the internal structures of the eye gradually. The method seems to be of value in the context of eye diseases diagnosing and treatment.

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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 syntheses and characterization of heterodi- and heterotrimetallic complexes of general formulas [Pd{[(eta5-C5H 3)-C(R)=N-R?]Fe[(eta5-C5H 4)-C(R)=N-R?]}Cl(PPh3)] [Pd{[(eta5-C5H3)C(C6H 5)=N-C6H5]Fe[(eta5-C 5H4)-C(O)=N-C6H5]}Cl(PPh 3)], and [Pd2{Fe[(eta5-C5H3)-C(R)= N-R?]2}Cl2(PPh3)2] {with R = H, CH3, or C6H5 and R?= phenyl or benzyl groups} are reported. The X-ray crystal structure of the meso-form of [Pd2{Fe[(eta5-C5H3)-C(CH 3)=N-C6H5]2}Cl2(PPh 3)2] (2b) is also 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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Real time measurement of time-correlated ion transport and volumetric changes in electroactive materials is necessary to understand and model mechanoelectrochemistry. Reversible reduction and oxidation of soft electroactive materials such as conducting polymers result in the deformation of the material due to ion transport into and out of the polymer backbone. In cells, ion transport and volumetric expansion are collectively responsible for homeostasis that is essential for life functions and hence, mechanoelectrochemistry of cells is essential to understand cell and developmental biology. The characterization methods required to investigate mechanoelectrochemistry require nanoscale spatial resolution for the imaging of a redox active site in a polymer or a small group of transmembrane proteins in a single cell. Towards this goal, we present an imaging technique using scanning electrochemical microscopy (SECM) hardware with shear-force (SF) feedback for high bandwidth mechanoelectrochemistry characterization. In this proceedings article, we demonstrate this technique referred to as surface-tracked scanning electrochemical microscopy technique (ST-SECM) that is realized by measuring the structural feedback of the glass electrode to position the electrode in 10s of nanometers above the surface of a polypyrrole membrane doped with dodecylbenzenesulfonate (PPy(DBS)). Two ultra-microelectrodes of controlled dimensions (of 20 mum and 30 mum glass diameter) were fabricated using a hydrofluoric acid etching technique and were used to generate a spatially correlated ion storage map of PPy(DBS). We compare the developed technique to a three-dimensional discrete scan over the surface and show that a ST-SECM technique produces a higher resolution and takes approximately 200 fewer minutes as compared to the conventional technique.

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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 family of 15 ferrocene derivatives has been prepared, most of which are reported for the first time. This includes FcCH2O-3-cholestanyl, 1; FcCH2O(CH2)13CH3, 2; FcCH2O(CH2)15CH3, 3; FcCH2O(CH2)17CH3, 4; FcCH2N[(CH2)17CH3]2, 5; FcCH2O(CH2)8OCH2Fc, 6; FcCH2O(CH2)12OCH2Fc, 7; FcCH2O(CH2)16OCH2Fc, 8; Fc(CH2)22Fc, 9; FcCH2-3,17-beta-estradioxy-CH2Fc, 10; Fc-1,1′-[COO(CH2)16CH3], 11; FcCONH(CH2)17CH3, 12; Fc-1,1′-{CON[(CH2)17CH3]2}2, 13; Fc-1,1′-(COO-3-dihydrocholesteryl), 14; and Fc-1,1′-(COO-3-cholesteryl), 15. Redox potentials for 1-15 have been determined and are in the range 400-450 mV for 2-6 (vs SSCE) and 509 mV for 1, 972 mV for 7, 806 mV for 8, 711 mV for 9, 941 mV for 10, and 945 mV for 11 (vs Ag/AgCl). Upon oxidation with Ce(IV), aqueous suspensions of compounds 1-5 and 7-10 formed stable vesicles after sonication. The charged monomers that formed vesicles afforded aggregates in the 2000-3000 A range that were characterized by laser light scattering and negative stain electron microscopy. In the absence of an oxidizing agent, vesicles failed to form from any of the 15 monomers even after prolonged sonication. Addition of 500 muM aqueous Na2S2O4 solution collapsed the vesicles formed from 1-5 and 7-10, and the original amphiphile monomers were detected afterward by thin layer chromatography. It was concluded from cyclic voltammetry that both ferrocene residues in 8 were oxidized. Vesicles formed from 7-10 represent the first examples of a redox-switched bolaamphiphile.

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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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57Fe NMR spectra of 20 ferrocene derivatives with natural abundance of 57Fe have been recorded by the conventional pulse Fourier transform technique using ferrocene as internal standard for the chemical shifts.Shift contributions of the substituents are discussed qualitatively.

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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