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1,1?-Disubstituted ferrocenes have been prepared and used as chelating ligands in the preparation of Cu(II) compounds with a variety of anions such as nitrate, sulfate, oxalate, and acetate. These compounds have been characterized by physical, spectral, and analytical methods. Screening of these derivatives against pathogenic bacterial species such as Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, and Klebsiella pneumoniae showed all of them to possess varied bactericidal activity.

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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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Interfacial energetics for n-type MoSe2 (Eg = 1.4 eV, direct) and photoelectrochemical conversion of light to electrical energy in the presence of Xn-/X- (X = Cl, Br, I) have been characterized in CH3CN electrolyte solution.Data for MoSe2 in H2O/I3-/I- are included for comparison, along with a comparison of MoSe2-based cells with MoS2- (Eg = 1.7 eV, direct) based cells.Cyclic voltammetry for a set of reversible (at Pt electrodes) redox couples whose formal potential, <*>, spans a range -0.8 to +1.5 V vs.SCE has been employed to establish the interface energetics of MoSe2.For the redox couples having <*> more negative than ca. -0.1 V vs.SCE, we find reversible electrochemistry in the dark at n-type MoSe2.When <*> is somewhat positive of -0.1 V vs.SCE, we find that oxidation of the reduced form of the redox couple can be effected in an uphill sense by irradiation of the n-type MoSe2 with <*>Eg light; the anodic current peak is at more negative potential than at Pt for such situations.The extent to which the photoanodic current peak is more negative than at Pt is a measure of the output photovoltage for a given couple.For <*> more positive than ca. +0.7 V vs.SCE it would appear that this output photovoltage is constant at ca. 0.4 V.For a redox couple such as biferrocene (<*>(BF+/BF) = +0.3 V vs.SCE) we find a photoanodic current onset at ca. -0.2 V vs.SCE; a redox couple with <*> = 1.5 V vs.SCE shows an output photovoltage of 0.43 V under the same conditions.The ability to observe (i) photoeffects for redox reagents spanning a range of <*>‘s that is greater than the direct Eg and (ii) constant photovoltage for a range of <*>‘s evidences an important role for surface states or carrier inversion such that a constant amount of band bending (constant barrier height) is found for a couple having <*> more positive than ca. +0.7 V vs.SCE.Conversion of <*> light to electricity can be sustained in CH3CN solutions of Xn-/X- (X = Cl, Br, I) with an efficiency that is ordered Cl > Br > I where n-type MoSe2 is used as a stable photoanode.In aqueous solution n-type MoSe2 is not a stable anode in the presence of similar concentrations of Br2/Br- or Cl2/Cl-, showing an important role for solvent in thermodynamics for electrode decomposition.In CH3CN, efficiency for conversion of 632.8-nm light to electricity has been found to be up to 7.5percent for Cl2/Cl-, 1.4percent for Br2/Br-, and 0.14percent for I3-/I-.Differences among these redox systems are output voltage and short-circuit current, accounting for the changes in efficiency.In H2O, I3-/I- yields a stable n-type MoSe2-based photoelectrochemical cell with an efficiency for 632.8-nm light a little lower that for the CH3CN/Cl2/Cl- solvent/redox couple system.Data for MoS2-based cells in the CH3CN/Xn-/X- solvent/redox couple systems show that the efficiency again depends on X: Cl > Br >I. …

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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 anodic electrochemical oxidations of ReCp(CO)3 (1, Cp = eta5-C5H5), Re(eta5-C 5H4NH2)(CO)3 (2), and ReCp*(CO)3 (3, Cp* = eta5-C 5Me5), have been studied in CH2Cl2 containing [NBu4][TFAB] (TFAB = [B(C6F5) 4]-) as supporting electrolyte. One-electron oxidations were observed with E1/2 = 1.16, 0.79, and 0.91 V vs ferrocene for 1-3, respectively. In each case, rapid dimerization of the radical cation gave the dimer dication, [Re2Cpgamma2(CO) 6]2+ (where Cpgamma represents a generic cyclopentadienyl ligand), which may be itself reduced cathodically back to the original 18-electron neutral complex ReCpgamma(CO)3. DFT calculations show that the SOMO of 1+ is highly Re-based and hybridized to point away from the metal, thereby facilitating the dimerization process and other reactions of the Re(II) center. The dimers, isolated in all three cases, have long metal-metal bonds that are unsupported by bridging ligands, the bond lengths being calculated as 3.229 A for [Re 2Cp2(CO)6]2+ (12 2+) and measured as 3.1097 A for [Re2(C 5H4NH2)2(CO)6] 2+ (222+) by X-ray crystallography on [Re 2(C5H4NH2)2(CO) 6][TFAB]2. The monomer/dimer equilibrium constants are between Kdim = 105 M-1 and 107 M-1 for these systems, so that partial dissociation of the dimers gives a modest amount of the corresponding monomer that is free to undergo radical cation reactions. The radical 1+ slowly abstracts a chlorine atom from dichloromethane to give the 18-electron complex [ReCp(CO) 3Cl]+ as a side product. The radical cation 1+ acts as a powerful one-electron oxidant capable of effectively driving outer-sphere electron-transfer reactions with reagents having potentials of up to 0.9 V vs ferrocene.

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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 diffusion rates of seven ferrocene derivatives have been estimated in polyelectrolyte PEG · LiClO4 by using non-steady-state chronoamperometry. The Dapp of ferrocene derivatives increases with temperature, and the dependency of Dapp on temperature obeys the Arrhenius equation. The Dapp of ferrocene derivatives decreases with increasing size of electroactive species. The DeltaDapp values of DT>Tm and DT Tm in the polyelectrolyte. On the other hand, the diffusion behaviour of ferrocene derivatives is qualitatively analyzed by using cyclic voltammetry. Copyright

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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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Four new diferrocenyl hydrazone?enone compounds were obtained through a two-step reaction process involving 1,1?-diacetylferrocene, hydrazides, and ferrocenecarboxaldehyde. The structural characterization of two compounds, 6 and 7, through single-crystal X-ray diffraction showed the presence of a stable eclipsed conformation with the two ferrocenyl moieties oriented in trans geometries. The electrochemical and metal-ion sensing properties of the diferrocenyl-bifunctionalized compounds were explored to understand their potential in electronic communication and as receptor molecules. Compounds 1,1?-[(eta5-C5H5)Fe(eta5-C5H4)CH=CHC(O)(eta5-C5H4)Fe{(eta5-C5H4)C(CH3)=N?N(H)C(O)?R}] [R = C6H4OH (6), C6H4N-p (7)], showed selective interactions with Pb2+cations and distinct binding interactions with bovine serum albumin (BSA) protein. The mode of the metal?receptor interaction was established through DFT studies. The redox properties of the diferrocenyl compounds with variable end groups revealed distinct electronic communication between the two electroactive groups.

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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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In heterogeneous catalysis, catalysts provide a surface to which reactants bind in a process of adsorption. In homogeneous catalysis, catalysts are in the same phase as the reactants. Computed Properties of C14H6FeO2. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 1273-94-5, Name is 1,1′-Diacetylferrocene

The first 2-phospha[3]ferrocenophanes containing stereogenic carbon atoms in the three-atom bridge have been synthesised from phenylphosphane by stereospecific ring-closing phosphanation reactions. Either alpha-substituted 1,1?-bis-(hydroxymethyl)ferrocenes or the corresponding 2-oxa-[3]ferrocenophanes have been used as diastereomerically pure starting materials. The resolution of 1,2,3-triphenyl-[2]phosphaferrocenophane has been achieved by chromatographic separation of the diastereomeric adducts of a chiral cyclopalladate complex. The X-ray crystal structures of two 2-phospha[3]ferrocenophane-borane complexes are also reported. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

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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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Acylferrocenes 2a-c reacted with ortho-aminoarylaldehydes 1a-e via the Friedlnder condensation reaction to afford the corresponding ferrocenylquinolines 3a-o in moderate yields in the presence of sodium ethoxide (30mmol%) under mild reaction conditions. Under the same reaction conditions, 1,1-diacetylferrocene 2d and 1,1-dipropionylferrocene 2e reacted with ortho-aminoaldehydes 1a-e to afford the corresponding 1,1-bis(substituted quinolin-2-yl)ferrocene derivatives 3p-t. The structures of compounds 3a-t were determined and characterized by infrared, 1H NMR, mass spectrometry, and elemental analysis. The crystal structures of 3e and 3q were determined by X-ray crystallography.

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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 probe based on ferrocene structure has been designed, synthesized and elucidated from the single crystal X-ray method. It demonstrated fluorescence response to Hg2+ and Cu2+ in CH3OH. The results indicated that the title complex could be applied in the multianalyte detection. Binding ability of receptor 3 in CH3OH was tested for various cations (Fe3+, Co2+, Cu2+, Zn2+, Cd2+, Hg2+, Pb2+, and Ba2+ in water). The computed binding constants for Hg2+ and Cu2+ indicated a distinct absorbance shift. The receptor is an attractive array due to its distinct absorbance shift profile in a semi-aqueous phase, making it applicable in biology, environmental sciences and material chemistry.

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Reference£º
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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Thiomethoxychalcone-based ligands bis[3,3-bis(methylsulfanyl)]-1,1?- eta5-ferrocenyl-2-propen-1-one (L1), 3,3-bis(methylsulfanyl)-1-eta5-ferrocenyl-2-propen-1-one (L 2), and 3-methylsulfanyl-3-sulfanyl-1-eta5-ferrocenyl-2- propen-1-one (L3) have been synthesized on the ferrocene backbone by varying the number of chalcone arms and thiomethoxy substitutents. The single-crystal X-ray crystallographic analyses of all three ligands are reported in which crystals of L1 were obtained as both syn and anti conformers and showed the conformational freedom of the two cyclopentadienyl (Cp) units. L1-L3 are studied extensively toward their applicability in the colorimetric sensing of metal ions in solution. The solution-state study of mono- and bis(thiomethoxy)ferrocenylchalcone- functionalized ligands L1 and L2 showed selective colorimetric sensing for Hg2+ over Li+, Na+, Ca2+, Mg2+, Cr2+, Mn2+, Fe 2+, Co2+, Ni2+, Cu2+, Zn 2+, Cd2+, and Au3+ in acetonitrile. In both cases, a selective color change from orange to purple was observed with Hg 2+ and the resultant solution showed the appearance of a new peak at 565 nm (epsilon = 3920 M-1 cm-1) for L1 and 600 nm (epsilon = 1140 M-1 cm-1) for L2 in the UV/vis experiments. The UV/vis titration profiles of L1 and L 2 indicate the formation of 2:1 (L1/Hg2+) and 1:1 (L2/Hg2+) initial complexations in solution. On the other hand, L3 with thiomethoxy- and thiol-functionalized ferrocenylchalcone showed no appreciable color change with Hg2+ under the same experimental conditions. Attempts were made to isolate single crystals of the resulting purple solution obtained in the cases of L1 and L2 with Hg2+. In both cases, crystals suitable for a single-crystal X-ray diffraction study were isolated in very low yield by a layer diffusion technique. The single-crystal structural investigations demonstrated the formation of a sulfide-encapsulated mercury thiolate cuboctahedron cluster, [Hg8S(SCH3)12] 2+, upon a selective chemodosimetric desulfurization reaction between Hg2+ and L1 or L2. Cyclic voltammetric studies also support the Hg2+-induced cleavage of thiomethoxy groups.

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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 visible absorption spectra and reduction potentials of 11 ferrocenes containing electron-withdrawing substituents were determined in an N-n-butylpyridinium chloride-aluminum chloride molten salt. When the substituent(s) on the cyclopentadienyl ring(s) of ferrocene were varied, the reduction potential was caused to range over 1.25 V, and the wavelength for maximum absorption of visible light was varied by nearly 200 nm. These changes are greater than have been observed for similar ferrocenes in other nonaqueous solvents. Evidence is presented for specific interactions of particular ferrocenes with the molten salt.

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Reference£º
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