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The surface of a screen-printed carbon electrode (SPCE) was modified by using amorphous carbon nitride (a-CNx) thin film deposited by reactive magnetron sputtering. Scanning electron microscopy and photoelectron spectroscopy measurements were used to characterise respectively the morphology and the chemical structure of the a-CNx modified electrodes. The incorporation of nitrogen in the amorphous carbon network was demonstrated by X ray photoelectron spectroscopy. The a-CNx layers were deposited on both carbon screen-printed electrode (SPCE) and silicon (Si) substrates. A comparative study showed that the nature of substrate, i.e. SPCE and Si, has a significant effect on both the surface morphology of deposited a-CNx film and their electrochemical properties. The improvement of the electrochemical reactivity of SPCE after a-CNx film deposition was highlighted both by comparing the shapes of voltammograms and calculating the apparent heterogeneous electron transfer rate constant.

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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 28 mono and disubstituted ferrocenes with a natural abundance of 57Fe have been measured relative to internal ferrocene.Most of the resonances appear at the high frequency side.The shielding influence of the various substituents is discussed qualitatively. 57Fe shifts are very sensitive to ring tilting as occurring in <3>ferrocenophanes. – Keywords: 57Fe Shifts; Hybridization influence on chemical shifts; Ring tilting

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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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Ferrocene-based metalloligands have various applications in material sciences due to their stability in air and redox active properties. Two ferrocene-based compounds, 1,2-bis(dimethyldithiocarbamate)ferrocene (1) and 1,2-bis(benzothiazol-2-ylthio)ferrocene (2), were synthesized from 1,1?-dibromoferrocene and the corresponding disulfides via two steps. The reaction of 1 with PdCl2(PhCN)2 formed a 1:1 metal:ligand complex, [PdCl2(1)]. Compounds 1, 2, and [PdCl2(1)] were structurally characterized by single-crystal X-ray diffraction, and their redox potentials were measured by cyclic voltammetry. Two pseudopolymorphs, ethanol-solvated 1(C2H5OH)0.33 and non-solvated 1, were obtained by recrystallization from ethanol. The Xray structure of [PdCl2(1)] showed that the Pd(II) center was chelated by 1 with two thioketone sulfur atoms; 1 showed two irreversible oxidationpeaks at 0.17 and 0.41 V (vs. Fe(Cp)2/Fe(Cp)2+), corresponding to oxidation of the two substituents and ferrocene, respectively. Conversely, 2 showed a quasi-reversible redox potential at E1/2 = 0.40 V, attributable to the ferrocene moiety. [PdCl2(1)] showed two irreversible oxidation peaks at 0.48 and 0.64 V and a reduction peak at 0.52 V (vs. Fe(Cp)2/Fe(Cp)2+).

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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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Electrochemical potential cycling of gold electrodes in commonly used redox active species to produce a nanostructured surface is introduced. A commercially available gold electrode when cycled in three redox active species including hexaammine ruthenium chloride, ferrocene methanol and ferricyanide shows rapid conversion of the surface into a nanostructured form within 50 cycles which usually requires hundreds of cycles in their absence. The active gold nanostructured electrode was characterized by cyclic voltammetry in acidic and alkaline electrolyte indicating the presence of different basal sites depending on the redox species employed. In addition, the active gold nanostructured surface shows higher electrocatalytic activity than the pristine polycrystalline gold electrode for glucose and ascorbic acid oxidation in alkaline 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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A mononuclear non-heme Mn(III)-aqua complex, [(dpaq)MnIII(OH2)]2+ (1, dpaq = 2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-yl-acetamidate), is capable of conducting hydrogen atom transfer (HAT) reactions much more efficiently than the corresponding Mn(III)-hydroxo complex, [(dpaq)MnIII(OH)]+ (2); the high reactivity of 1 results from the positive one-electron reduction potential of 1 (Ered vs SCE = 1.03 V), compared to that of 2 (Ered vs SCE = -0.1 V). The HAT mechanism of 1 varies between electron transfer followed by proton transfer and one-step concerted proton-coupled electron transfer, depending on the one-electron oxidation potentials of substrates. To the best of our knowledge, this is the first example showing that metal(III)-aqua complex can be an effective H-atom abstraction reagent.

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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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Vinyl silyl ethers and disiloxanes can now be prepared from aryl-substituted alkenes and related substrates using a silyl-Heck reaction. The reaction employs a commercially available catalyst system and mild conditions. This work represents a highly practical means of accessing diverse classes of vinyl silyl ether substrates in an efficient and direct manner with complete regiomeric and geometric selectivity.

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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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Synthetic approaches based on the direct borylation of ferrocene by BBr3, followed by boryl substituent modification, or on the lithiation of ferrocene derivatives and subsequent quenching with the electrophile FBMeS2, have given access to a range of ferrocene derivatized Lewis acids with which to conduct a systematic study of fluoride and cyanide binding. In particular, the effects of borane electrophilicity, net charge, and ancillary ligand electronics/cooperativity on the binding affinities for these anions have been probed by a combination of NMR, IR, mass spectrometric, electrochemical, crystallographic, and UV-vis titration measurements. In this respect, modifications made at the para position of the boron-bound aromatic substituents exert a relatively minor influence on the binding constants for both fluoride and cyanide, as do the electronic properties of peripheral substituents at the 1 ?- position (even for cationic groups). By contrast, the influence of a CH2NMe3 + substituent in the 2- position is found to be much more pronounced (by >3 orders of magnitude), reflecting, at least in part, the possibility in solution for an additional binding component utilizing the hydrogen bond donor capabilities of the methylene CH2 group. While none of the systems examined in the current study display any great differentiation between the binding of F- and CN- (and indeed some, such as FcBMeS2, bind both anions with equal affinity within experimental error), much weaker boronic ester Lewis acids will bind fluoride (but give a negative response for cyanide). Thus, by the incorporation of an irreversible redox-matched organic dye, a two-component [BMes2/B(OR)2] dosimeter system can be developed capable of colorimetrically signaling the presence of fluoride and cyanide in organic solution by Boolean AND/NOT logic.

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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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Electric Literature of 1271-51-8, Healthcare careers for chemists are once again largely based in laboratories, although increasingly there is opportunity to work at the point of care, helping with patient investigation. 1271-51-8, Name is Vinylferrocene, molecular weight is 203. molecular formula is C12H3Fe. In an Article,once mentioned of 1271-51-8

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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Characterizing paramagnetic complexes in solids is an essential step toward understanding their molecular functions. However, methodologies to characterize chemical and electronic structures of paramagnetic systems at the molecular level have been notably limited, particularly for noncrystalline solids. We present an approach to obtain connectivities of chemical groups and metal-binding structures for unlabeled paramagnetic complexes by 13C and 1H high-resolution solid-state NMR (SSNMR) using very fast magic angle spinning (VFMAS, spinning speed ?20 kHz). It is experimentally shown for unlabeled Cu(II)(Ala-Thr) that 2D 13CV1H correlation SSNMR under VFMAS provides the connectivity of chemical groups and assignments for the characterization of unlabeled paramagnetic systems in solids. We demonstrate that on the basis of the assignments provided by the VFMAS approach multiple13C-metal distances can be simultaneously elucidated by a combination of measurements of 13C anisotropic hyperfine shifts and 13C T1 relaxation due to hyperfine interactions for this peptide-Cu(II) complex. It is also shown that an analysis of 1H anisotropic hyperfine shifts allows for the determination of electron-spin states in Fe(III)-chloroprotoporphyin-IX in solid states.

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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 new form of high surface area bioelectrode, based on nanofibers of electrospun gold with immobilized fructose dehydrogenase, was developed. The gold fibers were prepared by electroless deposition of gold nanoparticles on an electrospun poly(acrylonitrile)-HAuCl4 fiber. The material was characterized using electron microscopy, XRD and BET, as well as cyclic voltammetry and biochemical assay of the immobilized enzyme. The electrochemical surface area of the gold microfibers was 0.32±0.04m2/g. Fructose dehydrogenase was covalently coupled to the gold surface through glutaraldehyde crosslinks to a cystamine monolayer. The enzyme exhibited mediated electron transfer directly to the gold electrode and catalytic currents characteristic of fructose oxidation in the presence of a ferrocene methanol mediator were observed. The limit of detection of fructose was 11.7muM and the KM of the immobilized enzyme was 5mM. The microfiber electrode was stable over 20 cycles with a 3.05% standard deviation. The response time of the sensor was less than 2.2s and reached half maximum value within 3.6s. The sensor was proven to be accurate and precise in both serum and popular beverages sweetened with high fructose corn syrup. The addition of glucose isomerase enabled the sensor to perform with glucose, thus expanding the available analyte selection for the sensor.

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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