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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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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 photolysis of 1,1?-diacylferrocenes Fc(COR)2 (Fc = Ferrocenyl, R = CH3,Ph) in the presence of 1,10-phenanthroline (phen) in deoxygenated acetonitrile under irradiation with visible light has been studied. In these photolysis systems the phen has two important roles to play: one is to stabilize the photo-liberated Fe2+ by coordination, and the other is to promote the photolysis through photo-ligand exchange. Under this condition the photoproducts were isolated in definite composition and characterized by single crystal X-ray diffraction, 1H NMR spectroscopy, IR spectroscopy, photolysis-cyclic voltammetry and elemental analysis. The mechanism of the reactions was demonstrated to be charge transfer from metal to acylcyclopentadienyl ring, leading to cleavage of the bond between them. The phen attacks the Fe2+ ion to give the stable tris (1,10-phenanthroline) iron(II) complex cation and the acylcyclopentadienyl ring detaches from the Fe2+ ion, giving the enolate anion in the outer sphere of the complex. Crystallographic data for photoproduct 1, [Fe(phen)3] (C5H4COCH3)2 ·CH3CN ·2H2O: triclinic, space group P-1 (No. 2), a=12.714(4), b=13.125(3), c= 14.946(5) A, alpha=106.45(1), beta=112.13(3), gamma=79.60(2). V=2208(1) A3, R = 0.041, RW = 0.052. Crystallographic data for photoproduct 2, [Fe(phen)3](C5H4COC6H 5)2 ·0.5C6H6 ·H2O: triclinic, space group P-1 (No. 2), a= 12.218 (4), b= 12.440 (3), c= 16.989 (2) A, alpha = 98.56(2), beta= 102.06(2), gamma= 100.98(3), V=2431(2) A3, R = 0.049, RW = 0.057.

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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 synthesis of a C2 symmetric 1,1? ,2,2?-tetrasubstituted ferrocene system was discussed. The route involved the reduction of ferrocenyl carbonyl compounds which gave access to a range of alcohols, alkenes, alkanes, ethers, and 2-oxa[3]ferrocenophanes depending on the precise conditions used. The loss of optical activity of 1,1?-bis(hydroxymethyl)ferrocenes and 1,1?-bis(hydroxymethyl)ruthenocenes, which had been prepared by asymmetric reduction, was demonstrated in an acidic medium by extensive 1H NMR studies.

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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

 

Sep-13 News The important role of 12180-80-2

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Friedel-Crafts acylations of ferrocene in 1-ethyl-3-methylimidazolium halogenoaluminate ionic liquids, [emim]I-(AlCl3)x are described.3 The effect of varying the “bulk” Lewis acidity of the ionic liquids used as solvents in these reactions and the effect of varying the relative amounts of acylating agent with respect to the amount of ferrocene in these reactions is also described. The use of a variety of different acylating agents in our studies demonstrates the scope of this reaction performed in these ionic liquid systems.

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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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Alkylferrocenes are obtained in excellent yields by ionic hydrogenation of ferrocenyl aldehydes and ketones using sodium boranuide and trifluoroacetic acid.

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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 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 12180-80-2, and how the biochemistry of the body works.Application In Synthesis of 1,1′-Dibenzoylferrocene

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1,1′-Dibenzoylferrocene reacts with tetraphosphorus decasulphide to yield, in addition to the expected 1,1′-bis(thiobenzoyl)ferrocene, a minor, yellow by-product (1) of composition C24H18FeS3.Crystals of (1) are monoclinic, space group P21/n with a = 11.769(3), b = 11.750(4), c = 14.835(2) Angstroem, beta = 98.63(1) deg, and Z = 4; the structure was refined from diffractometer data to an R value of 0.041.The structure was found to be that of 1,4-diphenyl-1,4-epithio-2,3-dithia<4>(1,1′)ferrocenophane, in which the two rings of the ferrocene nucleus are spanned by a 1,2,4-trithiolane ring.

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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 series of complexes of transition metal ions (Cr3+, Mn 2+, Co2+, Ni2+, Cu2+, Zn 2+) and of lanthanide ions (La3+, Nd3+, Gd 3+, Dy3+, Lu3+) with the anions of ferrocenylmethyl-L-cysteine [(C5H5)Fe(C5H 4CH(R)SCH2CH(NH3+)CO 2-] (L1) and with the dianions of 1,1?-ferrocenylbis(methyl-L-cysteine) [Fe(C5H 4CH(R)SCH2CH(NH3+) CO 2-)2] (R = H, Me, Ph) (L2) as N,O,S-donors were prepared. With the monocysteine ferrocene derivative L 1 as ligands complexes [MIIL12] or [CrIIIL12]Cl type complexes are formed whereas the bis(cysteine) ligand L2 yields insoluble complexes of type [ML2]n, presumably as coordination polymers. The magnetic moments of [MnIIL2]n, [PrIIIL 2]n(OH)n and [DyIIIL 2]n(OH)n exhibit “normal” paramagnetism.

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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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Ferrocenes bearing acyl substituents in the cyclopentadienyl rings [Fe(eta5-C5H4COR)(eta5-C 5H5)] and [Fe(eta5-C5H 4COR)2] (R = CH3, CF3 and Ph) were examined as new driers for solvent-borne alkyd binder. All studied ferrocenes were found to be active catalysts for cross-linking reaction of the alkyd. These iron(II) compounds give solid polymeric films with hardness and drying time comparable to the commercial cobalt(II) drier. Acetyl- and benzoyl-substituted ferrocenes show an excellent synergic effect with the cobalt drier giving hard polymeric films within short drying time. The kinetics of the alkyd autoxidation was followed by FTIR spectroscopy. Spin-trapping ESR technique has proven the important role of the ferrocenium cation upon decomposition of hydroperoxides by ferrocene-based driers. The peroxy and alkoxy radicals, appearing in drying process, were resolved by the new spin trap methyl-N-mesityl nitrone.

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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 syntheses and characterization of heterodi- and heterotrimetallic complexes of general formulas [Pd{[(eta5-C5H 3)-C(R)=N-R?]Fe[(eta5-C5H 4)-C(R)=N-R?]}Cl(PPh3)] [Pd{[(eta5-C5H3)C(C6H 5)=N-C6H5]Fe[(eta5-C 5H4)-C(O)=N-C6H5]}Cl(PPh 3)], and [Pd2{Fe[(eta5-C5H3)-C(R)= N-R?]2}Cl2(PPh3)2] {with R = H, CH3, or C6H5 and R?= phenyl or benzyl groups} are reported. The X-ray crystal structure of the meso-form of [Pd2{Fe[(eta5-C5H3)-C(CH 3)=N-C6H5]2}Cl2(PPh 3)2] (2b) is also described.

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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 series of mono- and 1,1′-diheteroatom-substituted ferrocene derivatives as well as acylated ferrocenes was prepared efficiently by a unified strategy that consists of selective mono- and 1,1′-dilithiation reactions and subsequent coupling with carbon, phosphorus, sulfur and halogen electrophiles. Chemical oxidation of the ferrocene derivatives by benzoquinone, 2,3-dichloro-5,6- dicyanobenzoquinone, AgPF6, or 2,2,6,6-tetramethyl-1-oxopiperidinium hexafluorophosphate provided the corresponding ferrocenium salts. The redox potentials of the synthesized ferrocenes were determined by cyclic voltammetry, and it was observed that all new ferrocenium salts have stronger oxidizing properties than standard ferrocenium hexafluorophosphate. An initial application of selected derivatives in an oxidative bicyclization revealed that they mediate the transformation under considerably milder conditions than ferrocenium hexafluorophosphate. Quantum chemical calculations of the reduction potentials of the substituted ferrocenium ions were carried out by using a standard thermodynamic cycle that involved the gas-phase energetics and solvation energies of the contributing species. A remarkable agreement between theory and experiment was found: the mean average deviation amounted to only 0.030-V and the maximum deviation to 0.1-V. This enabled the analysis of various physical contributions to the computed reduction potentials of these ferrocene derivatives, thereby providing insight into their electronic structure and physicochemical properties. 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