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An efficient synthetic approach to the synthesis of ferrocenyl heterocyclic derivatives in dilute solutions has been developed. The new compounds were characterised by means of IR, UV, and 1H NMR, spectroscopy and elemental analysis. The structure of complex I was studied by X-ray single-crystal diffraction. The synthesized compounds have a potential of new enzyme models and molecular recognition hosts.

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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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Influence of molecular geometry, type of exchange-correlation functional, and contraction scheme of basis set applied at the iron nuclei have been tested in the calculation of 57Fe Moessbauer isomer shifts and quadrupole splittings for a wide range of ligand types, as well as oxidation and spin states, in inorganic and organometallic systems. It has been found that uncontraction of the s-part of Wachter’s full-electron basis set at the iron nuclei does not appreciably improve the calculated isomer shifts. The observed correlations for all tested sets of geometries are close to each other and predominantly depend on the employed exchange-correlation functional with B3LYP functional being slightly better as compared to BPW91. Both hybrid (B3LYP) and pure (BPW91) exchange-correlation functionals are suitable for the calculation of isomer shifts in organometallic compounds. Surprisingly, it has been found that the hybrid B3LYP exchange-correlation functional completely fails in accurate prediction of quadrupole splittings in ferrocenes, while performance of the pure BPW91 functional for the same systems was excellent. This observation has been explained on the basis of relationship between the amount of Hartree-Fock exchange involved in the applied exchange-correlation functional and the calculated HOMO-LUMO energy gap in ferrocenes. On the basis of this explanation, use of only pure exchange-correlation functionals has been suggested for accurate prediction of Moessbauer spectra parameters in ferrocenes.

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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 self-assembly and structural characterization of the new ferrocene-containing dicopper(II) double helicate [Cu2L12] (1) and related copper(II) complex [CuL2(CH3CN)] [ClO4]2 (2) and silver(I) complexes [AgL2(CH3CN)][BF4] (3) and [AgL2] [BF4](4) have been achieved. These complexes are derived from inexpensive and easy-to-prepare ferrocene-containing bisbidentate Schiff-base ligands H2L1, [(C6H4)(OH)CHNNC(CH3) (C5H4)]2Fe, and L2, [(C5H4N)CHNNC(CH3) (C5H4)]2Fe. The neutral double-helical dicopper(II) complex 1 crystallizes in a polar space group. The two ferrocene-containing ligands strand interwined about each other and around the two tetrahedral copper ions in a double-helical fashion, with the Cu&mellip;Cu separation being 9.45 A . The four metal centers are coplanar and form a slightly distorted rhombus with sides of ca. 5.8 A . Reaction of the ligand L2 and copper(II) constructed a mononuclear copper complex, 2. X-ray structural analysis reveals that the copper(II) atom is coordinated in a distorted square pyramidal geometry, with four nitrogen atoms from the two bidentate bind sites forming the basal plane; the acetonitrile nitrogen atom occupies the apical position. The molecular structure of the silver(I) complex 3 is quite similar to that of copper complex 2, with the silver(I) surprisingly coordinated in a square pyramidal geometry. The silver(I) atom in mononuclear silver complex 4 is coordinated in a new square planar fashion. The result presented here shows that while the ligand (L1)2- can bridge two metal ions to give a double helicate with Cu(II), the ligand L2 acts as a tetradentate ligand chelate to a single metal center in its structurally characterized complexes with Cu(II) and Ag(I). Crystal structures of the free ligand H2L1 and L2 are also reported for comparison.

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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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Treatment of the a-dimethylamino[3]ferrocenophane derivative 3 with n-butyllithium results in a directed o-metalation at the adjacent Cp ring of the ferrocene unit to selectively yield the (R*,R*,p-S*) diastereomer 4. Similarly, lithiation of rac-12 gives (R*,p-S*)-13. Both these compounds form mesc-type dimers in the crystal that feature a central C2Li2 four-membered-ring moiety. Compound 13 crystallizes with excess n-butyllithium to form a (13-n-BuLi) dimer that was also characterized by X-ray diffraction. Directed lithiation of the nonbridged ferrocene derivative l-(dimethylaminobenzyl)ferrocene (16) with tertbutyllithium resulted in an opposite stereoselectivity to yield (R*,p-R*)-17, which forms a chiral dimeric structure in the solid state, as was revealed by its X-ray crystal structure analysis.

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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 redox behavior and kinetic parameters of five ferrocene derivatives were investigated in 1M LiPF6 in 50:50 volume percent EC:EMC, a typical electrolyte used in lithium-ion batteries. Using cyclic voltammetry (CV) and rotating disk electrode voltammetry (RDE) techniques, the effect of electron donating and withdrawing substituents on each derivative was evaluated from the view point of the Hammett substituent constant. We found that electrochemical rate constants of the ferrocene derivatives can be related to the Hammett equation which gives an accurate approximation for predicting the oxidation potential of redox shuttles when changes are desired in their electron donating and electron withdrawing properties by means of functional group substitution. Our results show that the exchange current density and reaction rate for oxidation decrease as the electron withdrawing property of the substituent increases. It is also shown that electron donating and electron withdrawing property of a substituent affect the exchange current density and electrochemical oxidation reaction rate obeying a trend opposite to that of the Hammett substituent constants (sigma). The correlations found here are expected to improve the ability to systematically design chemical overcharge protection reagents through judicious substitution of functional groups on redox shuttles.

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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 new family of heterometallic compounds 3-6 containing ferrocenyl and platinum(ii) centers has been synthesized by reaction of 1-beta- aminoethylferrocene (1) and 1,1?-bis(beta-aminoethyl)ferrocene (2) with Pt(ii) precursors. Using K2[PtCl4] as the Pt(ii) source, the cis-square-planar neutral compounds [Fe{eta5-C 5H4(CH2)2NH2} 2PtCl2] (3) and [{Fe(eta5-C5H 4(CH2)2NH2)(eta5-C 5H5)}2PtCl2] (5) were obtained. Reaction of cis-[PtCl2(dmso)2] with 1 and 2 resulted in the displacement of dmso and chloride ligands from the platinum coordination sphere, affording the cationic and neutral compounds [Fe{eta5- C5H4(CH2)2NH2} 2Pt(dmso)Cl]Cl (4) and [Fe(eta5-C5H 4(CH2)2NH2)(eta5-C 5H5)Pt(dmso)Cl2] (6). Compounds 3-6 were thoroughly characterized using multinuclear (1H, 13C, 195Pt) NMR, IR spectroscopy, ESI mass spectrometry and elemental analysis. Single-crystal X-ray analysis of heterometallic 6 confirmed the cis geometry of the molecule and revealed that the platinum atom is held in a perfect square-planar geometry. The electrochemical behaviour of the heterometallic compounds 3-6, which has been examined by cyclic (CV) and square wave (SWV) voltammetries in dichloromethane and dmso solution, is characterized by the reversible one-electron oxidation of the ferrocene moieties. The results of the biological activity studies revealed that the organometallic complex 5 is active against all cell lines with GI50 values in the range 1.7-2.3 muM. When compared to the standard anticancer drug cisplatin, heterotrimetallic 5, possessing two aminoethylferrocenyl units coordinated to the Pt(ii) center, showed a greater activity profile in the colon cancer cell line. Cell cycle studies revealed that the new mixed compound exhibits a mechanism of action different to cisplatin.

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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 conversion of acetylferrocene or diacetylferrocene into ethynylferrocene 1 or diethynylferrocene 4, respectively, is achieved in good yield in a one-pot synthesis using Negishi’s reagent.The diethynylferrocene is isolated as its trimethylsilylderivative 5.The complexes 1 and 5 undergo various nucleophilic substitution reactions, resulting in new ferrocenyl derivatives.

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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

Chemical engineers work across a number of sectors, processes differ within each of these areas, but chemistry and chemical engineering roles are found throughout, creation and manufacturing process of chemical products and materials. Application of 1273-94-5. 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 discontinuous temperature dependence of Moessbauer recoil-free fraction observed in diethylferrocene, reflects the transition from the glass state to the super-cooled liquid state followed by crystallization on heating the sample which was prepared by cooling quickly the liquid sample with liquid nitrogen.On cooling the crystallized diethylferrocene, the temperature dependence was similar to that found monoethylferrocene.

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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

As a society publisher, everything we do is to support the scientific community – so you can trust us to always act in your best interests, Related Products of 1273-94-5, and get your work the international recognition that it deserves. Introducing a new discovery about 1273-94-5, Name is 1,1′-Diacetylferrocene

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 iron 2p and carbon 1s near-edge X-ray absorption fine structure (NEXAFS) spectra of substituted ferrocene compounds (Fe(Cp-(CH3) 5)2, Fe(Cp)(Cp-COOH), Fe(Cp-COOH)2, and Fe(Cp-COCH3)2) are reported and are interpreted with the aid of extended Hiickel molecular orbital (EHMO) theory and density functional theory (DFT). Significant substituent effects are observed in both the Fe 2p and C 1s NEXAFS spectra. These effects can be related to the electron donating/withdrawing properties of the cyclopentadienyl ligands and their substituents as well as the presence of pi* conjugation between the cyclopentadienyl ligand and unsaturated substituents.

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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