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Regioselectivity of the HBF4-catalyzed ferrocenylalkylation of 2-mercaptobenzoxazole in two phase aqueous organic solvent mixture was studied. The reaction proceeds regioselectively at the heterocyclic nitrogen atom. Structures of the synthesized compounds were established by 2D NMR technique. Structure of 3-(1-ferrocenylbenzyl)benz[d]oxazol-2-thione was elucidated by X-ray diffraction.

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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 structures, electrochemical properties, enantiomeric separation of ferrocenyl (alkyl)pyrimidines and ferrocenyl(ethyl)adenine and their effects on the DNA synthesis in tumor cells were studied. Enantiomeric mixtures were separated by HPLC on modified cellu lose as the chiral selector. The electrochemical properties of compounds were studied by cyclic voltammetry. All compounds have reversible singleelectron redox transition in the region of 0.52-0.60 V, which belongs to ferrocene-ferrocenium with a positive shift compared to ferrocene (0.52 V). The molecular structure of 1N (ferrocenylbenzyl)5iodocytosine was studied by X-ray diffraction. 1-N (Ferrocenylethyl)adenine was studied for ability to inhibit the DNA synthesis in the human ovarian cancer cell culture by the 3H thymidine test.

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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 general method for the preparation of ferrocenylamines involves the reactions of ferrocenyl bromide, FcBr*, with the sodium salt of an amine or amide in the presence of copper(I)bromide/pyridine.The syntheses of diferrocenylphenylamine and triferrocenylamine, NFc2Ph and NFc3, respectively, are reported, and the hydrolysis of N-ferrocenyl acetamide to give ferrocenylamine, NH2Fc, is described.The system of the ferrocenyl- and/or phenyl-substituted derivatives of ammonia, NFcnX3-n (n=0-3; X=H, Ph), is characterised on the basis of mass, UV VIS and in particular of 1H and 13C NMR spectroscopic data.

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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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Disclosed are a metallocenyl dendrimer, an organic memory device using the metallocenyl dendrimer and a method for fabricating the organic memory device. The metallocenyl dendrimer may be composed of a dendrimer and metallocenes as redox species linked to the dendrimer. The organic memory device may possess the advantages of shorter switching time, decreased operating voltage, decreased fabrication costs and increased reliability. Based on these advantages, the organic memory device may be used as a highly integrated, large-capacity memory device.

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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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Isomeric phosphinoferrocene ligands, viz. 1?-(diphenylphosphino)-1-cyanoferrocene (1) and 1?-(diphenylphosphino)-1-isocyanoferrocene (2), show markedly different coordination behaviours. For instance, the reactions of 1 with [PdCl2(MeCN)2] and [(LNC)Pd(mu-Cl)]2 (LNC = [2-(dimethylamino-kappaN)methyl]phenyl-kappaC1) produced the ?phosphine? complexes [PdCl2(1-kappaP)2] (7) and [(LNC)PdCl(1-kappaP)] (8), and the latter was converted into the coordination polymer [(LNC)Pd(mu(P,N)-1)][SbF6] (9). Conversely, the reaction of 2 with [(LNC)Pd(mu-Cl)]2 involved coordination of the phosphine moiety and simultaneous insertion of the isocyanide group into the Pd-C bond, giving rise to the P,eta1-imidoyl complex [PdCl(Ph2PfcN?CC6H4CH2NMe2-kappa3C,N,P)] (10; fc = ferrocene-1,1?-diyl). Compound 10 was further transformed into the Fischer carbene [PdCl(Ph2PfcN(Me)CC6H4CH2NMe2-kappa3P,C,N)][BF4] (11) by methylation with [Me3O][BF4]. The reactions of 2 with Pd-Me and Pd(eta3-allyl) precursors also led to imidoyl complexes [Pd(mu-Cl)(Ph2PfcN?CR-kappa2C,P)]2 (R = Me: 12, R = allyl: 15), which were cleaved with PPh3 into the corresponding monopalladium complexes [PdCl(PPh3)(Ph2PfcN?CR-kappa2C,P)] (R = Me: 13, R = allyl: 16). The treatment of 12 and 15 with thallium(i) acetylacetonate (acac) produced [Pd(acac-O,O?)(Ph2PfcN?CR-kappa2C,P)] (R = Me: 17, R = allyl: 18). Through proton transfer, these complexes reacted with Ph2PCH2CO2H, ultimately producing bis-chelate complexes [Pd(Ph2PCH2CO2-kappa2O,P)(Ph2PfcN?CR)] (R = Me: 19, R = prop-1-enyl (sic!): 20). In addition, compound 13 was converted into the P-chelated carbene [PdCl(PPh3)(Ph2PfcN(Me)CMe-kappa2C,P)][BF4] (14). Compounds 10, 11, 13 and 14 were studied by cyclic voltammetry and by DFT computations.

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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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1′,6′-Bis(stearoyloxy)biferrocene was synthesized and its Langmuir-Blodgett film was prepared, in which film the cyclopentadienyl rings of a ferrocene nucleus were orientated perpendicular to the film surface.Oxiadtion of the biferrocene derivative gave the mixed velence monocation complex which formed a stable monolayer on water.

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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 have synthesized a novel disubslituted ferrocenyl compound [Fe(C 5H4CO(CH=CH)2C6H4NEt 2)2] (3) that displays a remarkable fluorescence quantum yield (1.1 × 10-1) in acetonitrile, and we have studied its capacity for calcium detection in depth using both electrochemical and optical techniques in this medium. The results of our NMR analysis reveal that the ligand-calcium interaction is CO-centered and that an uncommon equilibrium occurs between 3 and calcium triflate, involving five species of different stoichiometries. In contrast, our analysis of the UV-vis absorption data indicates that only three species of different stoichiometries are formed when calcium perchlorate is used with 3. Mass spectrometry measurements provide strong support for the formation of all these different species in solution. In addition, the electrochemical detection of calcium triflate by 3 leads to an irreversible FeII/ FeIII oxidation process with an unusual negative shift (-60 mV) caused by the nBu4NBF4 salt effect on the Ca2+-3 interaction process. Compound 3 can also be an original optical probe to detect calcium perchlorate over a wide range of salt concentration by UV-vis absorption spectroscopy. The most original and intriguing property of compound 3 is that it exhibits an unprecedented “multistep” fluorescence behavior upon addition of this salt.

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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 reaction of ferrocene-1,1′-dicarbaldehyde with 2-acetylpyridine at room temperature for 24 h results in the synthesis of 3,5-[1,1′-ferrocenediyl]-1,7-di(2-pyridylcarbonyl)heptane instead of the expected enone or 1,5-dicarbonyl. The crystal structure of this compound has been determined by single-crystal X-ray methods. The complex is electroactive and exhibits a reversible iron(II)/(III) process at +0.014 V vs 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

 

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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 1293-65-8. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 1293-65-8, Name is 1,1′-Dibromoferrocene

A selective and efficient catalytic method was developed for the synthesis of new styryl-conjugated silyl-ferrocene materials. The use of an effective palladium catalytic system [Pd(eta2-dba)(P(o-tolyl)3)2] (3) with a K3PO4 base solution allowed us to obtain new, reactive ferrocene olefins which can be used in various applications. In addition, using the stereo-control silylative coupling reaction we received unique new organosilicon trans-vinylene products with a built-in metallocene.

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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, structure and electronic properties of novel Group 6 Fischer alkoxy-bis(carbene) complexes are reported. The UV/Vis spectra of these species display two main absorptions at approximately 350 and 550 nm attributable to a ligand-field (LF) and metal-to-ligand charge-transfer (MLCT) transitions, respectively. The planarity of the system and the cooperative effect of both pentacarbonyl metal moieties greatly enhance the conjugation between the group at the end of the spacer and the metal carbene fragment provoking dramatic changes in the LF and MLCT absorptions. This is in contrast to related push-pull Fischer monocarbenes, where the position of the MLCT band remains mostly unaltered regardless the substituent attached to the donor fragment. In addition, the MLCT maxima can be tuned with subtle modifications of the electronic nature of the central aryl fragment in the novel A-pi-D-pi-A (A=acceptor, D=donor) systems. DFT and time-dependent (TD) DFT quantum chemical calculations at the B3LYP/def2-SVP level have also been performed to determine the minimum-energy molecular structure of this family of compounds and to analyse the nature of the vertical one-electron excitations associated to the observed UV/Vis absorptions as well as to rationalise their electrochemical behaviour. The ability of tuning up the electronic properties of the compounds studied herein may be of future use in material chemistry. 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