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Reaction of 1,1?-ferrocenedicarbonyl chloride with 3-ethyl-2,4-dimethylpyrrole in DCM produced the half-way product, namely, the ferrocene bis(2-ketopyrrole) derivative 2 and not the expected bis(dipyrromethene) compound. The 2-ketopyrrole compound readily reacted with BF3·Et2O to produce the bis(difluoropyrrolo)-oxaborole compound, FBF, as a red/brown solid which was characterised by X-ray crystallography. 57Fe Moessbauer spectra for 2 and FBF were consistent with low-spin iron(II) (d6) ferrocene derivatives. A cyclic voltammogram for 2 in acetonitrile revealed a reversible wave at +0.31 V vs. Fc+/Fc (ferrocene-based) and an irreversible wave at -2.38 V vs. Fc+/Fc (ketopyrrole-based). The electrochemical behaviour is severely perturbed by the chelation of the BF2 groups. Alterations to the electronic properties of 2 by formation of FBF are also evident in the absorption profiles. DFT calculations [B3PW91, 6-31G(3df)] support the observed changes in the electrochemistry findings and the Moessbauer spectroscopic data. Reaction of 1,1?-ferrocenedicarbonyl chloride with 3-ethyl-2,4-dimethylpyrrole produces the bis(ketopyrrole) compound. Chelation of BF2 to the ketopyrrole units forms the difluoropyrrolo-oxaborole.

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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 this study, new dendrimers with a ferrocene core were produced by means of a divergent method for the immobilization of the glucose oxidase enzyme (GOx). Pt(II)and Pt(IV)ions were attached to the terminal groups of dendrimers. Metal-containing dendrimers, [Fc(MGlu)2-Aph-Pt(II)]and [Fc(MGlu)2-Aph-Pt(IV)], were obtained using the ?template method? with aminophenol and Pt(II)/Pt(IV)cations. These compounds have been characterized by molar conductivity, magnetic susceptibility, FTIR, UV?Vis, 1H NMR and LC-MS methods. The GOx enzyme was immobilized on the Fc(MGlu)2, [Fc(MGlu)2-Aph-Pt(II)]and [Fc(MGlu)2-Aph-Pt(IV)]dendrimers, and the immobilized enzyme optimization parameters (substrate concentration, temperature, pH, reusability and storage capacity)were determined. Their Km (mM)and Vmax (mM.min?1)values were calculated from the Michaelis?Menten equation. The reusability of the immobilized glucose oxidase enzyme was investigated in an artificial urine medium. The research showed that [Fc(MGlu)2-Aph-Pt(II)]retains more than 61.23% of its initial activity after 10 successive cycles, which is a remarkable result.

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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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Reductive deoxygenation of acylferrocenes to the corresponding alkylferrocenes proceeded in excellent yields on utilizing a combination of sodium cyanotrihydroborate and boron trifluoride-diethyl ether.This method allows the synthesis of alkylferrocenes with functionalized tethers and is adaptable to large-scale preparations.

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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 syntheses of ferrocene- and ruthenocene-functionalized tetraazamacrocyclic ligands and their corresponding transition metal complexes are described. Reaction of N,N?-bis(2-aminoethyl)-1,3-propanediamine (2,3,2-tet) with 1,1?-diformylferrocene and 1,1?-diformylruthenocene produces the ligands fcmac and rcmac in 81-85% yield. Examination of their CuII, NiII, CoII, ZnII and Fe II/III complexes by IR, UV/Vis, EPR and Moessbauer spectroscopy as well as by electrochemical studies suggests electronic communication between the two metal centers of each complex. The molecular structure of [Cu II(fcmac)(FBF3)]BF4, determined by X-ray structure analysis, is reported and shows that the distance between the two metals is 4.54 A. Stability constants, determined by potentiometric titration, indicate that the copper(II) complexes are of similar stability as those with unfunctionalized tetraazamacrocyclic ligands (e.g. cyclam = 1,4,8,11-tetraazacyclotetradecane); stability constants of cobalt(II) complexes are about 2 log units smaller, those of nickel(II) and zinc(II) complexes are reduced by more than 10 log units. This selectivity is discussed on the basis of the structural studies. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.

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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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Chemical engineers ensure the efficiency and safety of chemical processes, adapt the chemical make-up of products to meet environmental or economic needs, and apply new technologies to improve existing processes. Application of 1271-48-3. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 1271-48-3, Name is 1,1′-Ferrocenedicarboxaldehyde

1-(Nitrophenyl) functionalized 2-(3-pyrazolyl)pyridines were obtained by a nucleophilic aromatic substitution and could be reduced to the corresponding aminophenyl substituted derivatives. These compounds can be used to co-ordinate transition metal sites or for the generation of building blocks for supramolecular chemistry. The solid state structure of a 1,1?- functionalized ferrocene, which was obtained following this route, is discussed in detail.

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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 crystal architecture, stability, and behavior with temperature of bis(formyl)ferrocene, [Fe(eta5-C5H4CHO)2], have been investigated by variable-temperature X-ray diffraction experiments, differential scanning calorimetry, and thermogravimetry experiments. [Fe(eta5-C5H4CHO)2] is present with two independent molecules with cisoid and transoid relative orientations of the two formyl groups in the crystals obtained from the reaction sequence (phase RT-1). The role of C-H- – -O interactions involving the formyl groups has been examined. When RT-1 is heated, the first irreversible phase transition to a plastic phase (phase HT) is observed at ca. 38C (311 K). When it is cooled, phase HT transforms into a new room-temperature phase (RT-2). Once RT-2 has been formed, the system switches reversibly between HT and RT-2 (transition temperature in the heating cycles ca. 35C), while RT-1 can no longer be obtained. Further heating of phase HT shows the occurrence of an exothermic reaction at ca. 150C (423 K) leading to the formation of a ferrocene-based polymer.

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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 first organometallic derivatives of tricyclic quinazoline derivatives are prepared by condensation of the active C-3 methylene group of 7H-deoxyvasicinones with ferrocenecarbaldehyde. By following this route the conjugated parent alkaloid and derivatives with nitro, amino, as well as some alkanoylamino groups at C-7 were attached at the ferrocene moiety, thereby significantly extending the pi system. In addition, the parent compound was subjected to the reaction by treatment with ferrocene-1,1?-dicarbaldehyde, giving rise to the double condensation product, which is only the second case of a 1,1?-disubstituted ferrocene derivative with two alkaloid substituents. A number of the compounds obtained were subjected to X-ray crystallographic analyses. In all cases, the substituents adopt a coplanar conformation with the ferrocene cyclopentadienyl ligands. The influence of the substituents at C-7 through the extended conjugated pi system on the iron atom is reflected by results of cyclic voltammetric measurements as well as by DFT calculations. 7H-Deoxyvasicinones are condensed with ferrocenecarbaldehyde and with ferrocene-1,1?-dicarbaldehyde to generate extended pi systems with coplanar conformations of the two moieties. The products are investigated by crystal structure analyses, cyclic voltammetry, and DFT calculations.

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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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From the reaction of [PtCl2(N-CMe)2] with FcC-N (1) (Fc = Fe(eta5-C5H4)(eta5-C 5H5)) complex [PtCl2(FcC-N)(N-CMe)] (2) was obtained, which on subsequent treatment with 1 gave trans-[PtCl 2(N-CFc)2] (trans-3). The latter complex and the appropriate cis isomer (cis-3) were also accessible when [PtCl2] or [PtCl2(N-CMe)2] is reacted with a 2.6-fold excess of 1. Appropriate treatment of [PtCl2(N-CMe)2] with two equivalents of 1-acetyl-1′-cyanoferrocene (4) produced trans-[PtCl 2(Fe(eta5-C5H4CN)( eta5-C5H4C(O)Me))2] (trans-5). Coordination polymer [PtCl2(Fe(eta5-C5H 4CN)2)]n (7) was obtained by combining [PtCl2(N-CPh)2] with [Fe(eta5-C 5H4CN)2] (6). However, when 7 was reacted with PPh3 for deaggregation, [PtCl2(PPh3) 2] was formed. Addition of FcC-CLi (8-Li) to trans-3 gave pentametallic trans-[Pt(C-CFc)2(NH-CnBuFc)2] (10) via trans-[Pt(C-CFc)2(N-CFc)2] (9). When trans-3 is reacted with two equivalents of nBuLi in the absence of FcC-CH (8), trans-[PtCl2(NH-CnBuFc)2] (11) was obtained, which decomposed to FcC(-NH)nBu (12), giving FcC(O)nBu (13). Electrochemical measurements of the nitrile platinum complexes show no redox separation for the oxidation of the Fc and Fe(eta5-C 5H4)2 moieties. Compared with the noncoordinated ferrocenecarbonitriles, a shift to higher potentials is observed. In contrast, for 10 four well-separated redox events (-185, -90, +460, +545 mV) were found, which could be assigned to the oxidation of the Fc units. UV-vis/NIR spectroscopy allowed to determine an IVCT absorption (numax = 6495 cm-1, epsilonmax = 270 L·mol-1·cm-1, Deltanu1/2 = 2270 cm-1) for 10+, classifying this mixed-valent species as a weakly coupled class II system according to Robin and Day, while no IVCT transitions were observed for 10n+ (n = 2, 3). The structures of trans-3, cis-3, 10, and FcC(O)tBu (15) in the solid state were determined by single-crystal X-ray diffraction. Although the bond distances and angles of trans-3 and cis-3 are similar, the cis isomer crystallizes as a dimer possessing Pt-Pt distances within the sum of the van der Waals radii.

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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

 

Discovery of 1,1′-Ferrocenedicarboxaldehyde

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Functionalization of ferrocenyl moieties with a cyanovinyl system using a unique solid-state synthetic method led to the formation of donor-acceptor type compounds with wide absorption in the visible region. A DSSC study using the ferrocenyl cyanovinyl compound as a dye with an electrolyte-free fabrication system showed an unprecedented open-circuit voltage (VOC) of 763-841 mV. DFT calculations were carried out to understand an unique electron transfer mechanism for the DSSC device which may be responsible for the high VOC.

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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 present invention provides two ferrocene pyridine derivative and its synthesis method, wherein ferrocene single arm pyridine derivatives FeL1 and ferrocene double-arm pyridine derivatives FeL2 can be used for Cu2 + And Cr3 + Detection. (by machine translation)

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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