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The reaction of Cp?2Zr(OtBu)Me (Cp? = C5H4Me) and [Ph3C][B(C6F 5)4] yields the base-free complex [Cp? 2Zr(OtBu)][B(C6F5)4] (6), which exists as Cp?2Zr(OtBu)(CIR)+ halocarbon adducts in CD2Cl2 or C6D 5Cl solution. Addition of alkenes to 6 in CD2Cl 2 solution at low temperature gives equilibrium mixtures of Cp?2- Zr(OtBu)(alkene)+ (12a-l), 6, and free alkene. The NMR data for 12a-l are consistent with unsymmetrical alkene bonding and polarization of the alkene C=C bond with positive charge buildup at Cint and negative charge buildup at Cterm. These features arise due to the lack of d-pi* back-bonding. Equilibrium constants for alkene coordination to 6 in CD2Cl2 at -89 C, K eq = [12][6]-1[alkene]-1, vary in the order: vinylferrocene (4800 M-1) ? ethylene (7.0) ? alpha-olefins > cis-2-butene (2.2) > trans-2-butene (<0.1). Alkene coordination is inhibited by sterically bulky substituents on the alkene but is greatly enhanced by electron-donating groups and the beta-Si effect. Compounds 12a-l undergo two dynamic processes: reversible alkene decomplexation via associative substitution of a CD2Cl2 molecule, and rapid rotation of the alkene around the metal-(alkene centroid) axis. You can also check out more blogs about1273-86-5 and wish help many people in the next few years. .Formula: C12H3Fe

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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Lipoic acid derivatives and pharmaceutical formulations containing lipoic acid derivatives are useful in the treatment and prevention of disease characterized by disease cells that are sensitive to lipoic acid derivatives.

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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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Graphene quantum dots (GQDs), derived from functionalized graphene precursors are graphene sheets a few nanometers in the lateral dimension having a several-layer thickness. They are zero-dimensional materials with quantum confinement and edge site effects. Intense research interest in GQDs is attributed to their unique physicochemical phenomena arising from the sp2- bonded carbon nanocore surrounded with edged plane functional moieties. In this work, GQDs are synthesized by both solvothermal and hydrothermal techniques, with the optimal size of 5 nm determined using high-resolution transmission electron microscopy, with additional UV-Vis absorption and fluorescence spectroscopy, revealing electronic band signatures in the blue-violet region. Their potential in fundamental (direct electron transfer) and applied (enzyme-based glucose biosensor) electrochemistry has been practically realized. Glucose oxidase (GOx) was immobilized on glassy carbon (GC) electrodes modified with GQDs and functionalized graphene (graphene oxide and reduced form). The cyclic voltammetry, differential pulse voltammetry, and electrochemical impedance spectroscopy are used for characterizing the direct electron transfer kinetics and electrocatalytical biosensing. The well-defined quasi-reversible redox peaks were observed under various electrochemical environment and conditions (pH, concentration, scan rate) to determine the diffusion coefficient (D) and first-order electron transfer rate (kET). The cyclic voltammetry curves showed homogeneous ion transport behavior for GQD and other graphenebased samples with D ranging between 8.45 × 10?9 m2 s?1 and 3 × 10?8 m2 s?1 following the order of GO < rGO < GQD < GQD (with FcMeOH as redox probe) < GOx/rGO < GOx/GO < HRP/GQDs < GOx/GQDs. The developed GOx-GQDs biosensor responds efficiently and linearly to the presence of glucose over concentrations ranging between 10 muM and 3 mM with a limit of detection of 1.35 muM and sensitivity of 0.00769 muA muM?1·cm?2 as compared with rGO (0.025 muA muM?1 cm?2, 4.16 muM) and GO (0.064 muA muM?1 cm?2, 4.82 muM) nanosheets. The relatively high performance and stability of GQDs is attributed to a sufficiently large surface-to-volume ratio, excellent biocompatibility, abundant hydrophilic edges, and a partially hydrophobic plane that favors GOx adsorption on the electrode surface and versatile architectures to ensure rapid charge transfer and electron/ion conduction (<10 ms). We also carried out similar studies with other enzymatic protein biomolecules on electrode surfaces prepared from GQD precursors for electrochemical comparison, thus opening up potential sensing applications in medicine as well as bio-nanotechnology. We very much hope you enjoy reading the articles and that you will join us to present your own research about 1273-86-5, you can contact me at any time and look forward to more communication. Related Products of 1273-86-5

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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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Air-stable primary phosphines were photopolymerized using phosphane-ene chemistry, the phosphorus analogue of the thiol-ene reaction, to fabricate a completely new class of polymer networks. It was demonstrated that the tunable thermal and physical properties accessible using thiol-ene chemistry could also be achieved using an analogous phosphane-ene reaction. At the same time, the presence of the 31P nucleus that is easily observed using NMR spectroscopy allowed the chemical structures of the networks to be directly probed using solid state NMR spectroscopy. Following its incorporation into the network, phosphorus offers the distinct difference and advantage of being able to undergo a diverse array of further derivatization to afford functional materials. For example, the networks were demonstrated to serve as effective oxygen scavengers and to bind transition metals (e.g., Pd). By using the air stable ferrocenyl phosphine (FcCH2CH2)PH2, redox-active networks were produced and these materials could be pyrolyzed to yield magnetic ceramics. Overall, this demonstrates the promise of phosphane-ene chemistry as an alternative to thiol-ene systems for providing functional materials for a diverse range of applications.

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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

 

Discovery of 1,1′-Ferrocenedicarboxaldehyde

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Functionalization of ferrocenyl moieties with a cyanovinyl system using a unique solid-state synthetic method led to the formation of donor-acceptor type compounds with wide absorption in the visible region. A DSSC study using the ferrocenyl cyanovinyl compound as a dye with an electrolyte-free fabrication system showed an unprecedented open-circuit voltage (VOC) of 763-841 mV. DFT calculations were carried out to understand an unique electron transfer mechanism for the DSSC device which may be responsible for the high VOC.

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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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A direct synthesis of alpha-alkylated arylacetamides from arylacetonitriles and primary alcohols has been accomplished for the first time. In the presence of the rhodium complex [Rh(cod)Cl]2/triphenylphosphine/potassium hydroxide system, the desired alpha-alkylated arylacetamides were obtained in 74-92% yield under microwave conditions. The experimental results in this paper are in sharp contrast with previous reports, where the coupling of arylacetonitriles and primary alcohols produced the alpha-alkylated arylacetonitriles. Mechanistic investigations show that arylacetonitriles are first alpha-alkylated with primary alcohols to produce alpha-alkylated arylacetonitriles, which are further hydrated with the water resulting from the alpha-alkylation step to produce alpha-alkylated arylacetamides. More importantly, this research shows the potential of developing completely atom-economical reactions that involve the hydrogen autotransfer (or hydrogen borrowing) process.

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The structures adopted by a range of hydrotris(3,5-dimethylpyrazolyl) methane complexes [ML2{HC(pz?)3}]+ (M = Rh, Ir; L2 = diene) have been investigated. There is low steric hindrance between ligands in [Rh(eta-nbd){HC(pz?)3}] + (nbd = norbornadiene) and [Rh(eta-dmbd){HC(pz?) 3}]+ (dmbd = 2,3-dimethylbuta-1,3-diene) resulting in kappa3 co-ordination of the pyrazolylmethane. The complexes [M(eta-cod){HC(pz?)3}]+ (cod = cycloocta-1,5-diene) (M = Rh, Ir) are kappa2 co-ordinated with the free pyrazolyl ring positioned above and approximately parallel to the square plane about rhodium or iridium. The HC(pz?)3 complexes undergo fast exchange of the co-ordinated and unco-ordinated pyrazolyl rings on the NMR spectroscopic timescale. However, for [Rh(eta-dmbd){HC(pz?) 3}]+, the fluxional process is slowed at low temperatures, so that inequivalent pyrazolyl rings may be observed. A mechanism for the fluxional process is proposed involving dynamic interconversion between isomeric forms in solution. The bonding mode of the HC(pz?)3 ligand can be determined by 13C NMR spectroscopy. The 13C chemical shifts (for the sp3 hybridised carbon of the ligand) show the general pattern, kappa3 < 71.5 ppm < kappa2. The electrochemical behaviour of the pyrazolylmethane complexes is related to the degree of structural change, which occurs on electron transfer and is compared with that of the pyrazolylborate analogues. The prevalence of solvent effects in heterogeneous catalysis in condensed media has motivated developing theoretical assessments of solvent structures and their interactions with reaction intermediates and transition states. Recommanded Product: 1273-94-5, you can also check out more blogs about1273-94-5

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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

 

Discovery of Vinylferrocene

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The method comprises the following steps: dissolving an olefin-based compound and a borane-based compound in a solvent, then adding a zirconium catalyst, reacting the compound in a protective atmosphere at a reaction temperature in 0~150 C a 5min~8h range of up to a reaction temperature in a range of up to a reaction temperature in a range of up to a reaction time and separating to obtain an alkenyl borate compound. The method is simple and convenient to operate, low in cost, high in atom economy of reaction and suitable for industrial production. (by machine translation)

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Treatment of [Fc-1-R1-1?-R2] (R1 = H, R2 = CH(O); R1 = H, R2 = CMe(O); R1 = R2 = CMe(O)) with LiC{triple bond, long}CCH2OLi (prepared in situ from HC{triple bond, long}CCH2OH and n-BuLi) affords the ferrocenyl-substituted but-2-yne-1,4-diol compounds of general formula [Fc-1-R1-1?-{CR(OH)C{triple bond, long}CCH2OH}] (R1 = R = H (1a); R1 = H, R = Me (1b); R1 = CMe(O), R = Me (1c)) in low to high yields, respectively (where Fc = Fe(eta5-C5H4)2). In the case of the reactions of [Fc-1-R1-1?-R2] (R1 = H, R2 = CH(O); R1 = R2 = CMe(O)), the by-products [Fc-1-R1-1?-{CR(OH)(CH2)3CH3}] (R1 = R = H (2a); R1 = CMe(O), R = Me (2c)) along with minor quantities of [Fc-1,1?-{CMe(OH)(CH2)3CH3}2] (3) are also isolated; a hydrazide derivative of dehydrated 2c, [1-(CMe{double bond, long}CHCH2CH2CH3)-1?-(CMe{double bond, long}NNH-2,4-(NO2)2C6H3)] (2c?), has been crystallographically characterised. Interaction of 1 with Co2(CO)8 smoothly generates the alkyne-bridged complexes [Fc-1-R1-1?-{Co2(CO)6-mu-eta2-CR(OH)C{triple bond, long}CCH2OH}] (R1 = R = H (4a); R1 = H, R = Me(4b); R1 = CMe(O), R = Me (4c)) in good yield. Reaction of 4a with PhSH, in the presence of catalytic quantities of HBF4 · OEt2, gives the mono- [Fc-1-H-1?-{Co2(CO)6-mu-eta2-CH(SPh)C{triple bond, long}CCH2OH}] (5) and bis-substituted [Fc-1-H-1?-{Co2(CO)6-mu-eta2-CH(SPh)C{triple bond, long}CCH2SPh}] (6) straight chain species, while with HS(CH2)nSH (n = 2,3) the eight- and nine-membered dithiomacrocylic complexes [Fc-1-H-1?-{cyclo-Co2(CO)6-mu-eta2-CH(S(CH2)n-)C{triple bond, long}CCH2S-}] [n = 2 (7a), n = 3 (7b)] are afforded. By contrast, during attempted macrocyclic formation using 4b and HSCH2CH2OCH2CH2SH dehydration occurs to give [Fc-1-H-1?-{Co2(CO)6-mu-eta2-C({double bond, long}CH2)C{triple bond, long}CCH2OH}] (8). Single crystal X-ray diffraction studies have been reported on 2c?, 4b, 4c, 7b and 8.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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New ferrocenyl-subtituted compounds containing two different central cores (isocyanurate and 1,3,5-phenylene) and extended by two kinds of branches bearing both vinyl ferrocenyl (1 and 3) and cross-conjugated ferrocenyl-chalcone (2, 4 and 5) as endgroups have been synthetized and characterized both spectroscopically and electrochemically. These molecules have been synthesized in order to investigate the electronic properties imparted by both types of branches when they are connected to the central core. For all compounds, electrochemical studies have showed a simultaneous oxidation of all ferrocene units present in each compound. For all of them, except for compound 2, a chemically reversible oxidation wave on the voltammograms has been observed. In contrast, for compound 2, a chemically irreversible oxidation wave is obtained. Moreover, the vinyl ferrocenyl derivatives have presented a lower redox peak potential with respect to ferrocene standard compound, and the ferrocenyl-chalcone bearing derivatives, in accordance with a change in the electron releasing capability of these endgroups, have been oxidized at a higher potential. Bathochromic shifts of the active transitions in Uv-Vis region have been observed, which are associated to the presence of carbonyl groups in those molecular structures containing it. These results are in agreement with theoretically calculated transition energies, which have been obtained for compounds 1 and 2 using Time Dependent Density Functional Theory (TD-DFT).

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