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Mo(CH-t-Bu)(NAr)(O-t-Bu)2 (1a) in THf/0.1 M [n-Bu4N]AsF6 is not oxidized at potentials up to 1.0 V and undergoes a reversible, one electron reduction at -2.16 V vs SCE at a Pt electrode. An analogous intiator containing a ferrocenylmethylidene ligand (1b) can be synthesized by treating 1a with vinylferrocene. Redox-active derivatives of norbornene, containing ferrocene (2) or phenothiazine (3), were prepared and polymerized by 1a or 1b to give living block copolymers containing the ring-opened norbornene derivatives. The living polymer was cleaved from the metal in a Wittig-like reaction with pivaldehyde, trimethylsilylbenzaldehyde, or octamethylferrocenecarboxaldehyde. Polydispersities for the longer block copolymers containing up to ?80 monomer units were found to be as low as 1.05 by GPC. In one case the polydispersity of a homopolymer made from the ferrocene-containing monomer was determined by FD-mass spectroscopy to be 1.06. DSC studies suggest that microphase formation occurs in the block copolymers, even in the case of relatively low molecular weight materials. Solution voltammetric studies of homo and block copolymers showed that the redox centers were electrochemically independent and that all centers exchanged electrons with the electrode. Neutral polymers became insoluble upon oxidation to a polycation, yielding an adsorbed polymer layer on the electrode that could then be cathodically stripped. This oxidative deposition process depended on the electrolyte and the polymer molecular weight but also could be controlled by the size of a nonelectroactive block in the block copolymers. Problems resulting from precipitation of the redox polymers could be circumvented by employing normal pulse voltammetry. Polymers containing redox centers in both end groups as well as in the polymer chain itself have been prepared and their nature confirmed in electrochemical studies.

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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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Three ferrocene derivatives carrying different kinds of nitroxide radicals (1-3) were prepared as dual redox compounds. All of them have distorted molecular conformations between a Cp unit of a ferrocene group and a nitroxide group and the largest dihedral angle between the units is observed in the PO derivative 3. A unique magnetic behavior with a spin gap is disclosed in the derivative 3, reflecting two-dimensional interactions between the paired spins. Each derivative has two oxidation potentials based on both ferrocene and nitroxide groups and multi-step charge-discharge processes are found for all derivatives with the first discharge capacity over 200 A h kg-1.

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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 invention discloses a ansa-ferrocene derivative of the tertiary amine and its preparation method and application. Its application in particular to the amount-of-substance ratio of 1:1 of the ansa-ferrocene derivative of the tertiary amine and the three (five fluoro phenyl) boron composition “hindered” Lewis acid alkali catalyst, the catalyst is applied to the obtained catalytic imine hydrogenation reduction reaction. The catalyst has good stability, to a certain extent can replace the heavy metal catalyst, can be from the source to prevent chemicals in on heavy metal pollution, it has better application value and potential social and economic benefits. (by machine translation)

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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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Metallocenyl carbinols FcCH2OH (1a) and RcCH2OH (1b) dissolved in sc-CO2 penetrate into the acidic Nafion film under 20 MPa and 80 or 35 C. After removal of pressure and leaving at room temperature, the crystals rapidly formed on the surface of the film, were identified as ethers McCH2OCH2Mc, Mc = Fc or Rc, by X-ray study. Mechanism of their formation is 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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We extend our approach of combination chemotherapy through a single prodrug entity (O’Neill et al. Angew. Chem., Int. Ed. 2004, 43, 4193) by using a 1,2,4-trioxolane as a protease inhibitor carbonyl-masking group. These molecules are designed to target the malaria parasite through two independent mechanisms of action: iron(II) decomposition releases the carbonyl protease inhibitor and potentially cytotoxic C-radical species in tandem. Using a proposed target “heme”, we also demonstrate heme alkylation/carbonyl inhibitor release and quantitatively measure endoperoxide turnover in parasitized red blood cells.

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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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Ferrocene-1,1′-dicarbaldehyde has been prepared in 70percent yield in a one-pot procedure from dilithioferrocene-TMEDA complex and dimethylformamide.

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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 series of novel copolymers consisting of a redox monomer, vinylferrocene, and an ion-conducting monomer, omega-methacryloyl-alpha-methoxy-oligo(ethylene oxide) (average molecular weight = 470), have been prepared by radical copolymerization and characterized.Ionic conductivity and redox activity of the copolymers, complexed with lithium perchlorate, have been explored by using complex impedance spectroscopy and solid state voltammetry with microelectrodes, respectively.The copolymer/salt complexes exhibit ionic conductivity of 1E-5 S cm-1 at room temperature and chemically reversible redox activity by themselves without any fluid solvents.The redox activity can be assigned to redox reactions of ferrocene sites in the bulk polymeric phases.The redox reactions are caused by propagation of oxidized (reduced) sites, generated at the electrode/copolymer interface, by electron transfer (electron hopping) reactions between mixed valent ferrocene/ferrocenium sites in the diffusion layer.Apparent electron diffusion coefficient for the electron transfer reactions, evaluated by potential step chronoamperometry, increases with increasing vinylferrocene composition in the copolymers.These copolymer/salt complexes are intrinsic redox conductors which exhibit appreciable ionic conductivity and redox activity by themselves without any fluid solvents and can be distinguished from conventional redox polymers.

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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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(Chemical Equation Presented) Chirality3: A new ferrocene-based diphosphine ligand is applied to the asymmetric hydrogenation of alpha-substituted cinnamic acids. The P-centered-, C-centered-, and planar-chiral ligand (RC,RC,SFc,S Fc,SP,SP)-1 displays unprecedented enantioselectivity in this Rh-catalyzed reaction (see scheme; cod = cycloocta-1,5-diene).

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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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Ferrocene-1,1′-diylbis(diphenylmethanol), , forms hydrogen-bonded host-guest adducts with a wide range of hydrogen-bond donors and acceptors.Adducts with a diol:guest ratio of 1:1 were formed by MeOH, EtOH, Me2SO, Me2NCHO, piperazine, and 4,4′-bipyridyl and 1:2 adducts by Me2SO, dioxane, pyridine and piperidine.The 1:1 adduct with MeOH has been shown to be triclinic, space group P<*> with a = 8.7624(3), b = 12.2797(6), c = 14.8773(8) Angstroem, alpha = 106.572(4), beta = 97.879(4), gamma = 100.873(4) deg with a final R of 0.044 for 4982 observed reflections.The structure consists of a centrosymmetric assembly of two molecules of diol and two molecules of the guest MeOH, hydrogen bonded together to form a chair conformation (OH)6 ring.The 1:2 adduct with pyridine has been shown to be monoclinic, space group C2/c with a = 16.6252(10), b = 11.1016(9), c = 20.9440(16) Angstroem, beta = 107.855(6) deg with a final R of 0.042 for 3260 observed reflections.In the structure the diol lies on a two-fold rotation axis with its hydroxyl hydrogens disordered and participating in both intramolecular O-H…O and intermolecular O-H…N hydrogen bonding with the two pyridine guest molecules.

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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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1,1?-Bis(4,2?:6?,4?-terpyridin-4?-yl)ferrocene (1) reacts with ZnCl2 to yield a double-stranded 1D-coordination polymer [{Zn2(1)Cl4}?3CHCl3]n. The 1,1?-functionalized ferrocene core adopts a cisoid-conformation, giving rise to a folded conformation for 1 and a double-stranded 1D-polymer chain. This contrasts with previously reported multi-stranded chains supported by 4,2?:6?,4?-terpyridine ligands in which the multiple-nature of the chain arises from multinuclear metal nodes.

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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