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Substituent effects in the iron 2p and carbon 1s edge Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy of ferrocene compounds

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.

Substituent effects in the iron 2p and carbon 1s edge Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy of ferrocene compounds

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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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The substitution chemistry of the tris(3,5-dimethylpyrazolyl)-methanerhodium complex [Rh(CO)2{HC(pz?)3}]+

The complex [Rh(CO)2{HC(pz?)3}][PF6], 1 +[PF6]- {HC(pz?)3 = tris(3,5-dimethylpyrazolyl)methane}, prepared by reacting [{Rh(CO)2(mu-Cl)}2] with HC(pz?)3 in the presence of Tl[PF6], has a distorted square pyramidal structure with a kappa3-HC(pz?)3 ligand. Carbonyl substitution with Lewis bases gives [Rh(CO)L{HC(pz?)3}] [PF6] {L = PPh3, 2+[PF6]-; L = AsPh3, 3+[PF6]-; L = P(o-tolyl)3, 4+[PF6]-}, which have square planar kappa2 structures, confirmed by X-ray crystallography for 2+[PF6]-. The cations 2+ and 3+ have the third pyrazolyl ring orientated pseudo-parallel to the square planar metal whereas 4+ more likely has the third ring orientated exo to that plane. One-electron oxidation of 2+ and 3+ gives the Rh(II) dications [Rh(CO)(PPh3){HC(pz?)3}]2+, 22+, and [Rh(CO)(AsPh3){HC(pz?)3}]2+, 32+, characterised by ESR spectroscopy. Complex 1+[PF6]- reacts with PhC?CPh to give [Rh(CO)(eta2-PhC?CPh)-{HC(pz?)3}] [PF6], 5+[PF6]-, in which the two-electron donor alkyne occupies an equatorial position in a trigonal bipyramidal kappa3 structure. With MeC?CR (R = Me or Et), 1+[PF6]- gives the kappa2 square planar complexes [Rh{eta4-C4Me2R2C(O)}{HC(pz? )3}][PF6] (R = Me, 6+[PF6]-; R = Et, 7+[PF6]-) in which the cyclopentadienone ligands are coordinated via two Rh-monoalkene bonds; the structurally characterised form of 7+ has the two alkyne units linked head-to-head with the CEt termini bound to the ketonic CO group. With HC?CPh or HC?CH, 1+ gives the octahedral, kappa3 rhodium(III) metallacyclopentadienes [Rh(CO)(eta1:eta1?-CHCRCHCR) {HC(pz?)3}][PF6] (R = Ph, 8+[PF6]-; R = H, 9+[PF6]-) with the two alkynes linked head-to-tail in 8+. The reaction of 1+ with HC?CH also gives the cycloheptatrienone (tropone) derivative [Rh{eta4-C6H6C(O)}{HC(pz?)3} ][PF6], 10+[PF6]-, with a kappa3 ligand and the cycloheptatrienone ligand bound to the metal via two Rh-C sigma-bonds and one Rh-monoalkene interaction.

The substitution chemistry of the tris(3,5-dimethylpyrazolyl)-methanerhodium complex [Rh(CO)2{HC(pz?)3}]+

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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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Novel anticancer and antibacterial organometallic polymer based on ferrocene as a building block and xanthone bioactive scaffolds: Synthesis, characterization, and biological study

Poly(azine ferrocene-triazole-xanthone amide) (PAFTXA) was successfully synthesized from azine ferrocene bisacetylene (AFcB) and 2,7-(N-2-azidoacetamide) xanthone (NAzX) by using click chemistry protocol. In this paper, innovative AFcB moiety incorporated in this procedure as a monomer. This monomer was prepared in three steps from ferrocene scaffold, and the synthetic processes were discussed in details. Characterization of the synthesized novel intermediate materials, monomer, and the resulting polymer was performed by nuclear magnetic resonance, Fourier transform infrared, thermal gravimetric analysis, differential scanning calorimetry, and ultraviolet-visible spectrophotometer. In addition, the in vitro antibacterial activity of the polymer was appraised against Gram-positive and Gram-negative bacteria by using minimum inhibitory concentration method. Moreover; antitumoral effects of synthesized polymer were evaluated on Hela, MCF-7, and Saos cancer cell lines and compared with normal fibroblast cell line by means of 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay. Promising antiproliferative effects were detected on both epitheloid and mesenchymal cancer cell lines depending on PAFTXA concentration and time. Survey on its characteristic features revealed the proficiencies of our prepared biomaterial such as its high thermal stability as well as valuable antitumoral and antibacterial capabilities that make it an appreciable candidate for further bioapplications.

Novel anticancer and antibacterial organometallic polymer based on ferrocene as a building block and xanthone bioactive scaffolds: Synthesis, characterization, and biological study

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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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1273-94-5, Name is 1,1′-Diacetylferrocene, belongs to iron-catalyst compound, is a common compound. SDS of cas: 1273-94-5In an article, once mentioned the new application about 1273-94-5.

Hydrogen-bonded Adducts of Ferrocene-1,1′-diylbis(diphenylmethanol): Crystal and Molecular Structures of Adducts with Methanol (1:1) and Pyridine (1:2)

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.

Hydrogen-bonded Adducts of Ferrocene-1,1′-diylbis(diphenylmethanol): Crystal and Molecular Structures of Adducts with Methanol (1:1) and Pyridine (1:2)

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Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Synthesis, spectroscopic studies of binuclear Ruthenium(II) carbonyl thiosemicarbazone complexes containing PPh3/AsPh3 as Co-ligands: DNA binding/cleavage

The ruthenium(II) ferrocenyl heterocyclic thiosemicarbazone complexes of the type [RuCl(CO)(EPh3)]2L (where E = P/As; L = binucleating monobasic tridendate thiosemicarbazone ligand) have been investigated. Strutural features were determined by analytical and spectral techniques. Binding of these complexes with CTDNA by absorption spectral study indicates that the ruthenium(II) complexes form adducts with DNA and has intrinsic binding constant in the range of 3.3 ¡Á 104 – 1.2 ¡Á 105 M?1. The complexes exhibit a remarkable DNA cleavage activity with CT-DNA in the presence of hydrogen oxide and the cleavage activity depends on dosage.

Synthesis, spectroscopic studies of binuclear Ruthenium(II) carbonyl thiosemicarbazone complexes containing PPh3/AsPh3 as Co-ligands: DNA binding/cleavage

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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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Synthesis, structural characterization, and properties of a new range of strained 2-aza[3]ferrocenophane ligands: Dual behavior as electrochemical sensors of metal ions or anions

The synthesis of structurally new types of strained 2-aza[3]ferrocenophanes, 9 and 10, which comprise a benzoquinuclidine framework incorporating a 1,1?-disubstituted ferrocene unit is reported. These compounds were prepared in four steps from the readily available 1,1?-diacetylferrocene and thoroughly characterized by spectroscopic means and electrochemical methods. The ligands 9 and 10 act as electrochemical sensors either of Mg2-, Zn2-, and Ni2+ cations (free ligands), where a new redox peak appears in the CV shifted 310-350 mV, or hydrogensulfate anion (protonated ligand) via a significant cathodic perturbation. The crystal structures of compounds 9 and 9b (9¡¤HClO4) have been determined by single-crystal X-ray methods. In the latter compound the anion and cation are associated onto ribbons parallel to the z axis by four hydrogen bonds.

Synthesis, structural characterization, and properties of a new range of strained 2-aza[3]ferrocenophane ligands: Dual behavior as electrochemical sensors of metal ions or anions

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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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Reference of 1273-94-5, Because a catalyst decreases the height of the energy barrier, its presence increases the reaction rates of both the forward and the reverse reactions by the same amount.1273-94-5, Name is 1,1′-Diacetylferrocene, molecular formula is C14H6FeO2. In a article£¬once mentioned of 1273-94-5

MOESBAUER STUDIES ON FERROCENE COMPLEXES. VIII. DIACETYLFERROCENE-METAL HALIDE COMPLEXES

Moesbauer parameters are reported for a series of diacetylferrocene (DAF) complexes with Lewis acids (AlCl3, SnCl4, FeCl3, TiCl4).All the complexes show a lowering of quadrupole splitting (QS) relative to uncomplexed DAF.The decreases in QS are discussed in terms of their stereochemistry and related to previous findings in the ferrocenyl ketone series. 119Sn Moessbauer data are presented for SnCl4 * DAF.

MOESBAUER STUDIES ON FERROCENE COMPLEXES. VIII. DIACETYLFERROCENE-METAL HALIDE COMPLEXES

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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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In homogeneous catalysis, the catalyst is in the same phase as the reactant. The number of collisions between reactants and catalyst is at a maximum.In a patent, 1273-94-5, name is 1,1′-Diacetylferrocene, introducing its new discovery. HPLC of Formula: C14H6FeO2

Solid state and solution structures of rhodium and iridium poly(pyrazolyl)borate diene complexes

The structures adopted by a range of poly(pyrazolyl)borate complexes [ML2Tpx] [M = Rh, Ir; L2 = diene; Tp x = Bp? {dihydrobis(3,5-dimethylpyrazolyl)borate}, Tp? {hydrotris(3,5-dimethylpyrazolyl)borate}, Tp {hydrotris(pyrazolyl)borate}, B(pz)4 {tetrakis(pyrazolyl)borate}] have been investigated. Low steric hindrance between ligands in [Rh(eta-nbd)Tp] (nbd = norbornadiene), [Rh(eta-cod)Tp] (cod = cycloocta-1,5-diene) and [Rh(eta-nbd)Tp?] results in kappa3 coordination of the pyrazolylborate but [M(eta-cod)Tp?] (M = Rh, Ir) are kappa2 coordinated with the free pyrazolyl ring positioned above and approximately parallel to the square plane about the metal. All but the most sterically hindered Tp x complexes undergo fast exchange of the coordinated and uncoordinated pyrazolyl rings on the NMR spectroscopic timescale. For [Rh(eta-cod){B(pz)4}], [Rh(eta-dmbd)Tp?] (dmbd = 2,3-dimethylbuta-1,3-diene) and [Rh(eta-cod)TpPh] {TpPh = hydrotris(3-phenylpyrazolyl)borate} the fluxional process is slowed at low temperatures so that inequivalent pyrazolyl rings are observed. The bonding modes of the Tp? ligand (but not of other pyrazolylborate ligands) can be determined by 11B NMR and IR spectroscopy. The 11B chemical shifts (for a series of Tp? complexes) show the general pattern, kappa3 < -7.5 ppm < kappa2 and the nu(BH) stretch kappa3 > 2500 cm-1 > kappa2. The electrochemical behaviour of the pyrazolylborate complexes is related to the degree of structural change which occurs on electron transfer. One-electron oxidation of complexes with Tp?, Tp and B(pz)4 ligands is generally reversible although that of [Ir(eta-cod)Tp] is only reversible at higher scan rates and that of [Ir(eta-cod){B(pz)4}] is irreversible. Of the complexes with the more sterically hindered TpPh ligand, only [Rh(eta-nbd)TpPh] shows any degree of reversible oxidation. The ESR spectra of a range of Rh(ii) complexes show coupling to both 14N and 103Rh nuclei in most cases but what appears to be coupling to rhodium and one hydrogen atom, possibly a hydride ligand, for the oxidation product of [Rh(eta-nbd)TpPh]. The Royal Society of Chemistry 2008.

Solid state and solution structures of rhodium and iridium poly(pyrazolyl)borate diene complexes

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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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Synthesis and liquid crystalline behavior of a series of ferrocene 1,1′-bis-azino-derivatives

A series of liquid-crystalline ferrocene derivatives, Fe2 (X = H, OH; n = 3 to 12), were obtained by the condensation of 1,1′-bishydrazondiacetylferrocene with p-alkoxybenzoyloxybenzaldehydes.According to DSC and polythermic microscopy, all of the compounds exhibit an enantiotropic nematic mesophase in the 150-230 deg C temperature range.A polycrystalline transition precedes the nematic transition.The liquid crystalline properties of the obtained compounds were investigated with respect to the number of carbon atoms in the terminal alkyl chain and the terminal hydroxy group.The composition and structure of the obtained compounds were determined by elemental analysis and IR and NMR spectroscopy. – Key words: liquid crystals; ferrocene; metallomesogenes.

Synthesis and liquid crystalline behavior of a series of ferrocene 1,1′-bis-azino-derivatives

Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data. Quality Control of 1,1′-Diacetylferrocene, If a proposed mechanism predicts the wrong experimental rate law, however, the mechanism must be incorrect.Welcome to check out more blogs about 1273-94-5, in my other articles.

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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 feature of reaction of 1,1?-diacetylferrocene with dimethylformamide dimethyl acetal leading to a new strategy of the synthesis of asymmetrical 1,1?-disubstituted ferrocene

The reaction of 1,1?-diacetylferrocene with the dimethylformamide dimethyl acetal proceeds regioselectively to afford [1-acetyl-1?-(1- dimethylamino-3-oxoprop-1-en-3-yl)]ferrocene, based on which new approaches to the synthesis of 1,1?-disubstituted unsymmetrical ferrocene derivatives via the reaction with nucleophilic reagents hydrazine hydrate, hydroxylamine, and amidines were developed.

A feature of reaction of 1,1?-diacetylferrocene with dimethylformamide dimethyl acetal leading to a new strategy of the synthesis of asymmetrical 1,1?-disubstituted ferrocene

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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