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The complex generated from 1/2 [Ir(OMe)(cod)]2 and 4,4?-di-tert-butyl-2,2?-bipyridine catalyzes the regioselective borylation of ferrocenes, CpMn(CO)3 and CpMo(CO)3CH 3 with a stoichiometric amount of B2pin2.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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A solvent free synthetic method using rice husk ash (RHA) as solid support has been designed for selective functionalization and preparation of novel 1,1?- unsymmetrically bi-functionalized ferrocenyl compounds. The selectively functionalized intermediate compound, Ferrocenyl-1-acetyl-1?-thiosemicarbazone, has been structurally characterized using single crystal X-ray diffraction technique which revealed distinct inter-molecular hydrogen bonding interactions across the thiosemicarbazone chains. Cytotoxic evaluation of five different unsymmetrically bi-functionalized thiosemicarbazone – hydrazone compounds showed potent activity against human leukemia (THP-1) cell line. The unsymmetrical ferrocenyl compounds also showed strong BSA and DNA binding interactions and reversible redox properties.

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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 chromotropic ferrocenyl chalcone with two pyrenyl groups (Fc-dPyr) is prepared and spectroscopically characterized. The X-ray structure analysis shows that the two pyrenyl groups are almost parallel to each other with a torsion angle of 5.57 and adopt a dimeric mode with a distance of 3.776 A? between them, ready to form an excimer. The solvatochromic fluorescence spectra indicate that the emission maxima observed in hydrogen-bonding donor (HBD) solvents (CHCl3, EtOH and MeOH) exhibit a strictly linear relationship with the normalized ETN value, while those in a non-HBD solvent (CH3CN) do not. The molecular chemosensor activity of Fc-dPyr is highly selective toward Fe(III) ions over Fe(II) ions. The fluorescence emission intensity of Fc-dPyr steeply decreases in the presence of Fe(III) ions as an oxidant, but not in the presence of Fe(II) ions.

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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 report about a series of mono-nuclear and bi-nuclear complexes with acyclic as well as macro-cyclic ligands, which have been synthesized with Schiff base ligands in tri- tetra and pentadentate forms. The bonding sites on complex formation are mainly the azomethine groups and/or imide nitrogen, ketonic oxygen or sulphur atoms. Complexes of two series of Schiff base ligands, H 2 La and H2 Lb derived from the reaction of 2,6-diacetyl pyridine with semicarbazide, replaced by or thiosemicarbazide with the metal ions, Co(II), Ni(II), Cu(II), VO(IV) and UO2(VI) have been prepared. 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 also synthesized and react with the transition metal ions, copper(II), nickel(II), cobalt(II), and Zinc(II) in the molar ratio 1:1. The structures of these ligands as well as the related complexes are elucidated by different spectroscopic methods. Solvatochromic behavior of copper(II) mixed ligand complexes of 3-acetylcoumarine (3-ACoum) and dinitrogen bases (L), with the general formula Cu(3-ACoum)(L)Xn; where n = 2, L = N,N,-Rfnet-temp?, N?-tetramethylethylenediamine (tmen), 1,10-phenanthroline (phen), 2,2?-bipyridine (bipy) and X = ClO 4-, BF4- or NO3- their synthesis and characterization by elemental analysis, IR, UV-Vis, electron spin resonance spectra, magnetic susceptibility and conductivity measurements is reported. The d-d absorption bands of tmen-complexes in weak donor solvents show the formation of square planar or square pyramidal geometries, whilst the strong donor solvents yield octahedral complexes. The observed solvatochromism is mainly due to the solute-solvent interaction between the chelate cation and the solvent molecules and the spectra displayed the possibility of using these complexes as Lewis base indicators. The Coats-Redfern equation can be used to calculate the kinetic and thermodynamic parameters for the different thermal decomposition steps of some complexes. Cyclic voltagrammes of Co(II) and Ni(II) show quasi-reversible peaks and characterize the redox properties and the nature of the electroactive species of the complexes. Biochemically, both 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,
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 synthetic procedure based on the aza-Wittig reaction of alpha-azidoacetyl ferrocene or 1,1?-bis(alpha-azidoacetyl)ferrocene with mono-, di-, and triacyl chlorides and triphenylphosphine has been developed to prepare the new homotrimetallic ferrocene complexes 6, 9, and 10 containing at least two oxazole rings in the conjugation chain. Complexes 9 and 10 exhibited three and two reversible redox processes, respectively, indicating significant electrostatic interaction between the iron centers in these complexes. Protonation properties of complexes 9-13 have been assessed by use of 1H NMR and cyclic voltammetry measurements.

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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 enantiomerically pure dibromoferrocene 3 [(Sp,S p)-1,1?-dibromo-2,2?-di(isopropyl)ferrocene], equipped with two iPr groups in alpha positions, was prepared using known “Ugi amine” chemistry. Species 3 was targeted in order to gain access to new [1]ferrocenophanes ([1]FCPs) to be used as monomers for ring-opening polymerization. The iPr groups on the sandwich unit were introduced to stabilize bridging moieties, as well as to increase solubilities of targeted metallopolymers. The planar chiral dibromide 3 can quantitatively be lithiated at 0 C [2 equiv nBuLi, hexanes/thf (9:1), 30 min]. Salt-metathesis reactions with respective element dichloride species gave chiral [1]FCPs with a variety of bridging moieties [ERx=Ga[2-(Me2NCH 2)C6H4] (4 a), SiMe2 (4 b), SntBu2 (4 c), BNiPr2 (4 d)]. The new [1]FCPs were fully characterized including single-crystal X-ray analysis. The stabilizing iPr groups on the Cp rings increase the thermal stabilities of 4 b-d compared to known [1]FCPs, equipped with the same bridging moieties. All three compounds 4 b-d are volatile and could be isolated by vacuum sublimation. Our new approach to [1]FCPs has the potential to overcome many of the existing difficulties in ferrocenophane chemistry, such as limited stability of starting monomers and low solubilities of resulting polyferrocenes. Closing the gap: The preparation of [1]ferrocenophanes with a variety of bridging elements was accomplished by using chiral ferrocene derivatives (see scheme). The isopropyl groups on the sandwich unit serve as protective and solubilizing moieties. The new synthetic approach is superior to the common synthesis of [1]ferrocenophanes, when dilithioferrocene-tmeda is used as the starting material. Copyright

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1,1?-Diacetylferrocene bis(p-toluenesulfonylhydrazone) and its complex with divalent palladium of composition Pd2LCl2 were synthesized. Infrared, electronic, and 1 H NMR spectroscopy indicate that the semichelate has a cyclopaladinized structure. It is suggested that several forms of the complex exist in solution. Copyright

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A series of ferrocene-containing mono- and bis-dihydropyrimidines (DHP’s) were prepared by boric acid mediated three-component Biginelli reactions of formyl- and 1,1?-diformylferrocene, 1,3-dioxo-components and urea. A few further transformations including hydrogenolysis of a benzyl 4-ferrocenyl-DHP-5-carboxylate were also performed. Novel cis-fused saturated pyrimido[4,5-d]pyrimidine-2,7(1H,3H)-diones incorporating [3]-ferrocenophane moiety were constructed by means of iron(III)-catalyzed Biginelli-like condensations of 1,1?-diformylferrocene with urea and in situ generated methyl ketone-derived silyl enol ethers. The structures of the new compounds were established by IR and NMR spectroscopy, including HMQC, HMBC and DEPT measurements.

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Palladium-catalyzed enantioselective C(sp2)-H activation of ferrocenyl ketones is achieved through utilizing catalytic, inexpensive l-tert-leucine as a chiral transient directing group. The transformation allows rapid access to ferrocene scaffolds simultaneously possessing planar- and stereogenic central chirality, widely applied in the ferrocene-based chiral ligand families.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Cymantrenyl Schiff base compounds [(CO)3Mn{(eta5- C5H4)C(CH3)N-N(H)C(O)R}] (4-7) (R = C 6H4-OH, C5H4N-p, C6H 5, C5H4N-o) have been synthesized by room temperature reaction and their structural characterization was performed by single crystal X-ray diffraction studies. Room temperature reaction of mono- and di-acetyl ferrocene with salicyloyl and isonicotinyl hydrazides led to the formation of the some organometallic Schiff base compounds containing monosubstituted, disubstituted and unsymmetrically substituted ferrocenyl fragments, [(eta5-C5H5)Fe{(eta5- C5H4)C(CH3)N-N(H)C(O)-R}] (8, 9), [Fe{(eta5-C5H4)C(CH3)NN(H)C(O)R} 2] (10, 12) (R = C6H4-OH, C5H 4N), [{(eta5-C5H4)COCH 3}Fe{(eta5-C5H4)C(CH 3)NN(H)C(O)(C5H4N)}] (11) and [Fe{(eta5-C5H4)C(CH3)N-N(H)C(O) (C5H4N)}{(eta5-C5H 4)C(CH3)NN(H)C(O)C6H4-OH}] (13) respectively. Antibacterial studies and electrochemical analysis were carried out for some of the compounds. Molecular structure determination was performed for compounds 4, 5, 8 and 9 by single crystal X-ray diffraction technique.

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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