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Two series of mono-nuclear complexes with tetradentate macrocyclic Schiff base ligands, derived from the condensation of 1,1′-diacetylferrocene with 1,3-diaminopropanein in the molar ratio 1:1 and 1:2 have been prepared. The structures of these ligands were elucidated by different spectroscopic methods. The two Schiff base ligands react with copper(II), nickel(II), cobalt(II), and Zinc(II) metal ions in the molar ratio 1:1. The structures of complexes were identified by elemental analyses, infrared, electronic spectra, 1H-NMR,13C-NMR, magnetic susceptibility, conductivity measurement and TGA analysis. The ligands and the complexes show growth inhibitory activity against pathogenic bacteria and plant pathogenic fungi.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Treatment of 1,1?-diacetylferrocene (4) with dimethylamine and TiCl4 yielded the unsaturated dimethylamino-substituted [3]ferrocenophane product 5. Its catalytic hydrogenation gave the corresponding saturated [3]ferrocenophane system 6 (trans/cis ? 7:1). The rac-[3]ferrocenophane amine 6 was partially resolved (to ca. 80% ee) by means of L- or D-O,O?-dibenzoyltartrate salt formation. Treatment of 4 with the pure (R)- or (S)-methyl(1-phenylethyl)amine (8)/TiCl4 gave the corresponding optically active unsaturated [3]ferrocenophane amines (R)-(+)-9 and (S)-(-)-9, respectively. Their catalytic hydrogenation again proceeded trans-selectively, giving the corresponding saturated diastereomeric [3]ferrocenophane amines (1R,3R,5R)-10a and (1S,3S,5R)-10b [starting from (R)-9], their enantiomers ent-10a and ent-10b were obtained from (S)-9, but with a poor asymmetric induction (10a/10b < 2:1). Quaternization of 6 (CH3I) followed by amine exchange using (R)- or (S)-methyl(1-phenylethyl)amine (8), respectively, proceeded with overall retention. Subsequent chromatographic separation gave the pure diastereoisomers (1R,3R,5R)-10a and (1S,3S,5R)-10b [from (R)-8, ent-10a and ent-10b from (S)-8] in > 60% yield. Subsequently, the benzylic (1-phenylethyl) auxiliary was removed from the nitrogen atom by catalytic hydrogenolysis to yield the enantiomerically pure (> 98%) ([3]ferrocenophanyl)methylamines (1R,3R)-11 and (1S,3S)-11, respectively, which were converted into the corresponding dimethylamino-substituted [3]ferrocenophanes (1R,3R)-6 and (1S,3S)-6. Each enantiomer from the following enantiomeric pairs was isolated in its pure form and characterized by X-ray diffraction: (R)-9/(S)-9; (1R,3R,5R)-10a/(1S,3S,5S)-10a; (1R,3R,5S)-10b/(1S,3S,5R)-10b; (1R,3R)-11/(1S,3S)-11. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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The result showed that such a combination of chemo- and biocatalysis improved the catalytic yield more than two times compared with that of sole metal catalysis. We will look forword to the important role of 1273-94-5, and how the biochemistry of the body works.Computed Properties of C14H6FeO2

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X-Ray structural studies on the redox pair [Cr(CO)2(eta-PhC?CPh)(eta-C6Me5H)] z (z = 0 and 1) show that one-electron oxidation of the neutral complex results in a shortening of the Cr-Calkyne bonds and a lengthening of the Cr-C(O) bonds, consistent with depopulation of a HOMO antibonding with respect to the metal-alkyne interaction. Oxidation leads to an increase in the substitutional lability of the Cr-CO bonds so that [Cr(CO)2-(eta-RC?CR)(eta-C6Me6)] + (R = Ph or C6H4OMe-p) reacts with Lewis bases to give [Cr(CO)L(eta-RC?CR)(eta-C6Me6)]+ {L = CNXyl, P(OMe)3 and P(OCH2)3CEt}, X-ray studies on which show a rotation of the alkyne to align with the remaining Cr-CO bond. ESR spectroscopic studies on [Cr(CO)L(eta-RC?CR)(eta-C6Me6)]+ show delocalisation of the unpaired electron onto the alkyne ligand, consistent with its description as a three-electron donor. The cations [Cr(CO)L(eta-RC?CR)(eta-C6Me6)]+ undergo both one-electron reduction and oxidation, and chemical oxidation of [Cr(CO){P(OCH2)3CEt} (eta-p-MeOC6H4C?CC6H4OMe-p)( eta-C6Me6)]+ with AgPF6 gives the dication [Cr(CO){P(OCH2)3CEt}(eta-p-MeOC6H4 C?CC6H4OMe-p)(eta-C6Me6)] 2+. Thus the two-electron alkyne of [Cr(CO)2-(eta-RC?CR)(eta-C6Me6)] is converted into the four-electron alkyne of [Cr(CO)L(eta-RC?CR)(eta-C6Me6)]2+ by an ECE (E = electrochemical, C = chemical) process in which all of the intermediates have been fully characterised.

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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 kinetic facility of charge transfer was studied by cyclic voltammetry (CV) at Sn-doped indium oxide (ITO) electrode/acetonitrile interfaces for 18 one-electron outer-sphere redox systems. The results were compared with Pt, and the relative trends in redox kinetics were analyzed from a phenomenological viewpoint. The strong dependency of redox kinetics at the ITO surface on the location of electrolyte energy levels (redox potential) argues against the complete transparency of the space-charge layer in ITO to electron tunneling processes. The new results seem to be consistent with a model proposed by previous authors, which considers mediation of electron tunneling by deep-lying donor states in the space-charge region. For positive-lying redox systems, this mediation step is rate determining.

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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 have determined a convenient method for the bulk synthesis of high-purity ferric heme-nitrosyl complexes ({FeNO}6 in the Enemark-Feltham notation); this method is based on the chemical or electrochemical oxidation of corresponding {FeNO}7 precursors. We used this method to obtain the five- and six-coordinate complexes [Fe(TPP)(NO)]+ (TPP2- = tetraphenylporphyrin dianion) and [Fe(TPP)(NO)(MI)]+ (MI = 1-methylimidazole) and demonstrate that these complexes are stable in solution in the absence of excess NO gas. This is in stark contrast to the often-cited instability of such {FeNO}6 model complexes in the literature, which is likely due to the common presence of halide impurities (although other impurities could certainly also play a role). This is avoided in our approach for the synthesis of {FeNO}6 complexes via oxidation of pure {FeNO}7 precursors. On the basis of these results, {FeNO}6 complexes in proteins do not show an increased stability toward NO loss compared to model complexes. We also prepared the halide-coordinated complexes [Fe(TPP)(NO)(X)] (X = Cl-, Br-), which correspond to the elusive, key reactive intermediate in the so-called autoreduction reaction, which is frequently used to prepare {FeNO}7 complexes from ferric precursors. All of the complexes were characterized using X-ray crystallography, UV-vis, IR, and nuclear resonance vibrational spectroscopy (NRVS). On the basis of the vibrational data, further insight into the electronic structure of these {FeNO}6 complexes, in particular with respect to the role of the axial ligand trans to NO, is obtained.

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The ligands 1-ethoxycarbonyl-3-ferrocenyl-propane-1,3-dion and ferrocene-1,1?-bis(2,4-dioxo-butanoic acid ethylester) have been prepared by reaction of acetylferrocene or 1,1?-diacetylferrocene and diethyl oxalate. They yield neutral chelates with CuII, NiII, ZnII, CoII, and MnII. The acid dissociation constants of the ligands and the stability constants of their metal complexes including FeII complexes are reported. The structure of bis(1-ethoxycarbonyl-3-ferrocenyl-propane-1,3-dionato)copper(II) was determined by X-ray structure analysis. A cis arrangement with a nearly square planar coordination sphere at the Cu atom is found.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Four kinds of mannitol-based ketal-linked porous organic polymers (MKPOPs) were successfully synthesized through condensation reaction between aromatic acetyl monomers and mannitol, catalyzed by p-toluenesulfonic acid. The structure of resulting polymers was confirmed by Fourier transform infrared and solid-state 13C nuclear magnetic resonance spectrum measurements. The porosities of MKPOPs were investigated by gas adsorption experiments and the results indicate high carbon dioxide uptake (up to 11.5 wt% at 273 K and 1.0 bar) for MKPOPs due to the predominant microporous and hydroxyl-rich structures. Remarkably, MKPOPs exhibit excellent selective adsorption performances for carbon dioxide over methane (9.9-14.2, IAST at 273 K and 1.0 bar). These studies are of significant importance for MKPOPs and their potential application in selective gas adsorption.

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Oscillations in electrical current as a function of time have been observed in a specific temperature range in the samples of 1,1?-diacetylferrocene and 1,1?-ferrocenedicarboxylic acid with adsorbed ethanol vapor in a sandwich-type cell. The frequency of current oscillations has been found to decrease with bias voltage and sample temperature and to increase with vapor pressure. The frequency of current oscillations for the mono-group substituted derivatives is higher than the corresponding frequency for the derivatives having two substituted groups. Again, the frequency of oscillations for -COCH3 group substituted derivatives is higher than the corresponding value for -COOH group substituted derivatives. The observation of current oscillations is possibly associated with some kind of time dependent phase changes, arising from the structural nonrigidity of the molecules, in the solid-ethanol vapor system at the sample surface layer. The “ball-bearing” motion of the cyclopentadienyl rings of ferrocene unit, nature and number of substituted groups, cooperative interaction of the neighboring molecules influence the structural nonrigidity and hence the oscillatory behavior of current. Reasons are given for ruling out other models of current oscillations in semiconductors.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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The synthesis of two new donor-acceptor ferrocenyl derivatives with Meldrum’s acid based nonplanar acceptor substituents is presented. Both compounds are obtained in high yields in a simple reaction protocol under mild conditions using either 1-acetyl- or 1,1?-diacetylferrocene and Meldrum’s acid. Both products have been characterized spectroscopically, by single-crystal X-ray structure analysis, by electrochemical and UV/vis/IR spectroelectrochemical measurements, and by (TD)-DFT calculations. The spectroelectrochemical measurements disclose that the 2,2-dimethyl-1,3-dioxane-4,6-dione moiety is a moderately strong electron acceptor. (Figure Presented)

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We report the results of a systematic electrochemical study of the host-guest supramolecular adducts between ferrocene (Fc), ferrocenium cation (Fc+), and other mono- and disubstituted ferrocene derivatives with different beta-cyclodextrins (CD) in mixed organic-aqueous media. The influence on the formation constants (Kf) of the organic cosolvent, the different substituents on Fc, and the type of CDs are evaluated. NMR and conductometry responses of ferrocenium cation solutions in the presence of CD confirm the weak propensity of Fc+ to enter into the cyclodextrin cavity. The Kf value generally decreases as the steric bulk and the rigidity of Fc substituents increases, consistent with an inclusion model in which the Fc fits into the CD cavity in an axial mode while the substituent protrudes out. Interestingly, the addition of sulfated beta-CD shifts the redox Fc/Fc+ couple toward cathodic values, indicating that the oxidized, cationic form Fc+ is more strongly bound to the sulfated cyclodextrin than neutral Fc, probably by means of electrostatic interaction with the external -SO3- functionalities.

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