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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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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,
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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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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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(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,
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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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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,
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Self-cross-linkable ferrocenyl-containing polymethylhydrosiloxanes were synthesized. Karstedt’s catalyst and cis-[PtCl2(BnCN)2] were examined as cross-linking catalysts at room temperature for the reaction between Si?H groups of the ferrocenyl-containing polymethylhydrosiloxanes. Cis-[PtCl2(BnCN)2] is an effective catalyst that allows cross-linked ferrocenyl-containing silicones (silicone rubbers) to be obtained with no visible mechanical defects (bubbles or cracks) compared with Karstedt’s catalyst. The ferrocene content of the ferrocenyl-containing silicone rubbers was found to be approximately 50 wt.% by energy-dispersive X-ray analysis. Compared with cross-linked non-modified polymethylhydrosiloxanes, the ferrocenyl-containing silicone rubbers exhibited improved tensile properties (the tensile strength increased from 0.47 to 0.75 MPa) and a 1.5?2.5 times lower cross-linking degree. The surface resistivity of the ferrocenyl-containing silicone rubbers (50 wt.% ferrocenyl units) was approximately 7 × 109 Omega/?, which was 10,000 times lower than that of pure polymethylhydrosiloxane. The obtained flexible electroactive ferrocenyl-containing silicone rubbers can potentially be applied as coatings for electronic and electrostatic-sensitive devices, interfaces, and sensors.

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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 report the synthesis and full characterization of the entire haloferrocene (FcX) and 1,1?-dihaloferrocene (fcX2) series (X = I, Br, Cl, F; Fc = ferrocenyl, fc = ferrocene-1,1?-diyl). Finalization of this simple, yet intriguing set of compounds has been delayed by synthetic challenges associated with the incorporation of fluorine substituents. Successful preparation of fluoroferrocene (FcF) and 1,1?-difluoroferrocene (fcF2) were ultimately achieved using reactions between the appropriate lithiated ferrocene species and N-fluorobenzenesulfonimide (NFSI). The crude reaction products, in addition to those resulting from analogous preparations of chloroferrocene (FcCl) and 1,1?-dichloroferrocene (fcCl2), were utilized as model systems to probe the limits of a previously reported “oxidative purification” methodology. From this investigation and careful solution voltammetry studies, we find that the fluorinated derivatives exhibit the lowest redox potentials of each of the FcX and fcX2 series. This counterintuitive result is discussed with reference to the spectroscopic, structural, and first-principles calculations of these and related materials.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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