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[1.1.1]Propellane is a highly strained tricyclic hydrocarbon whose reactivity is dominated by addition reactions across the central inverted bond to provide bicyclo[1.1.1]pentane derivatives. These reactions proceed under both radical and two-electron pathways, hence, providing access to a diverse array of products. Conversely, transition metal-catalyzed reactions of [1.1.1]propellane are underdeveloped and lack synthetic utility, with reported examples generally yielding mixtures of ring-opened structural isomers, dimers, and trimers, often with poor selectivity. Herein, we report that nickel(0) catalysis enables the use of [1.1.1]propellane as a carbene precursor in cyclopropanations of a range of functionalized alkenes to give methylenespiro[2.3]hexane products. Computational studies provide support for initial formation of a Ni(0)-[1.1.1]propellane complex followed by concerted double C-C bond activation to give the key 3-methylenecyclobutylidene-nickel intermediate.

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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

 

Discovery of 1,1′-Dibromoferrocene

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A facile synthetic approach is reported for the synthesis of dissymmetric 1,2-ferrocenediyl Lewis acids and mixed acid-base pairs including the first example of a 1-phosphino-2-borylferrocene; the use of non-racemic electrophiles allows for the isolation of single diastereomer products.

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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 paper reports on the investigation of the electrochemical behavior of a thin gold film electrode coated with silicon dioxide (SiOx) layers of increasing thickness. Stable thin films of amorphous silica (SiOx) were deposited on glass slides coated with a 5 nm adhesion layer of titanium and 50 nm of gold, using plasma-enhanced chemical vapor deposition (PECVD) technique. Scanning electrochemical microscopy (SECM) and electrochemical impedance spectroscopy (EIS) were used to investigate the electrochemical behavior of the interfaces. In the case of SECM, the influence of the SiOx thicknesses on the electron transfer kinetics of three redox mediators was investigated. Normalized current-distance curves (approach curves) were fitted to the theoretical model in order to find the effective heterogeneous first order rate constant (keff) at the sample. EIS was in addition used to confirm the diffusion barrier character of the SiOx interlayer.

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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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A facile synthesis of new conjugated oligo-ferrocenyl compounds is described. The synthetic method consists of a two step procedure, which combines olefination by the Wittig procedure and Pd-mediated C-C coupling, leading to high yields of tri- and penta-ferrocenyl complexes. The crystal structures of the 1,1?-bissubstituted ferrocenyl precursors are described. The electrochemical analysis of the compounds obtained, reveals that the peripheral ferrocenyl units display an equivalent redox behavior, with a large separation of the peak corresponding to the central ferrocenyl unit.

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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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Hyphenated techniques have become an important tool in modern analytical research. Among detection techniques, mass spectrometry (MS) plays a dominant role, but efficient analyte separation prior to MS detection is usually desirable, as it provides the basis for reliable qualitative and quantitative determination. However, electrochemical methods offer very versatile approaches for selective sample pretreatment or analyte conversion. This review summarizes recent instrumental analytical developments, which resulted in a special kind of a hyphenated system: electrochemistry-capillary electrophoresis-MS (EC-CE-MS). We discuss the analytical characteristics of this approach and compare them with those of other techniques coupling EC with separation techniques and MS.

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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 work describes the formation of a mixed organic layer covalently attached to a carbon electrode. The strategy adopted is based on two successive electrochemical reductions of diazonium salts. First, bithiophene phenyl (BTB) diazonium salt is reduced using host/guest complexation in a water/cyclodextrin (beta-CD) solution. The resulting layer consists of grafted BTB oligomers and cyclodextrin that can be removed from the surface. The electrochemical response of several outer-sphere redox probes on such BTB/CD electrodes is close to that of a diode, thanks to the easily p-dopable oligo(BTB) moieties. When CD is removed from the surface, pinholes are created and this diode like behavior is lost. Following this, nitrophenyl (NP) diazonium is reduced to graft a second component. Electrochemical study shows that upon grafting NP insulating moieties, the diode-like behavior of the layer is restored which demonstrates that NP is grafted predominately in the empty spaces generated by beta-CD desorption. As a result, a mixed BTB/NP organic layer covalently attached to a carbon electrode is obtained using a stepwise electrochemical reduction of two diazonium compounds.

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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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Both human and horse fibrinogen are heme-binding proteins, and horse fibrinogen also exhibits heme-mediated ferritin binding. This study found that bovine and human fibrinogen are heme-mediated ferritin-binding proteins and demonstrated direct binding of bovine ferritin to protoporphyrin (PPIX) and its derivatives or to Zn ions. Binding of bovine and human fibrinogen to bovine spleen ferritin coated on microtiter plate wells was detected using an anti-human fibrinogen antibody, and this binding was inhibited in a dose-dependent manner by hemin (iron-PPIX) and also inhibited by Zn-PPIX. PPIX showed less of an inhibitory effect on the binding of bovine and human fibrinogen to bovine ferritin. The inhibitory effect of Sn-PPIX was similar to that of PPIX, but with respect to human fibrinogen, PPIX did not inhibit the binding of human fibrinogen to ferritin. Bovine fibrinogen immobilized on CNBr-activated Sepharose 4B beads showed affinity for hemin, Sn-PPIX, Zn-PPIX, and iron-free PPIX in the order Sn-PPIX < iron-free PPIX < hemin < Zn-PPIX. The fibrinogen beads also directly bound to zinc ions. These results suggest that bovine fibrinogen is a heme- and zinc-binding protein and that binding of circulating mammalian fibrinogen to ferritin is heme mediated. If you are interested in 16009-13-5, you can contact me at any time and look forward to more communication. The potential utility of systematic synthetic strategy will be applicable to efficient generations of chemical libraries of compounds to find ‘hit’ molecules. COA of Formula: C34H32ClFeN4O4

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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TCNQ and PVF polymer film electrodes have been studied by cyclic voltammetry.It has been established that cyclic voltammetric curves become distorted by uncompensated ohmic resistance for medium thick films at scan rates higher than 0.025 V/s.The effect of ohmic voltage drop can be practically eliminated by the use of an Electroflex GMK (Szeged) potentiostat using the interruption 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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The isolation and characterisation of a new macrocyclic hexaamine trans-6,13-bis(ferrocenylmethylamino)-6,13-dimethyl-1,4,8,11- tetraazacyclotetradecane (L2) bearing two ferrocenyl groups appended to its exocyclic amines is reported. The crystal structures of L2 and its dihydrochloride salt L2·2HCl·2H2O have been determined. In the latter case cation-anion hydrogen bonding is observed in the solid state. Substrate binding by the electroactive L2 in MeCN-CH2Cl2 solution has been examined by cyclic voltammetry and reveals the receptor electrochemically to recognise benzoate and chloride anions. The macrocyclic N-donors may also bind transition metal cations such as CuII and ZnII.

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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