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The capability of metallocene bridges as new organometallic magnetic couplers is evaluated by studying the family of diradicals 2 (M = Fe, Ru) consisting of two purely organic alpha-nitronyl aminoxyl radicals connected by a 1,1?-metallocenylene bridge. Preliminary studies performed with 2-metallocenyl-alpha-nitronyl aminoxyl monoradicals 1 (M = Fe, Ru, Os), as reference compounds, show the presence of a small spin density on the central metal of the metallocenes. This fact makes the metallocene units effective bridges to transmit magnetic interactions by a spin polarization mechanism. The study of the magnetic properties of diradicals 2 in the solid state and in diluted frozen solutions reveals the existence of an intramolecular antiferromagnetic exchange interaction between the radical subunits whose strength is highly dependent on the molecular conformation adopted by the diradical. As shown by crystal data and by ESR measurements, an intramolecular hydrogen bond between the two radical units forces the molecule to adopt a cisoid molecular conformation, which determines that the magnetic interaction occurs by a direct through-space interaction between the two SOMOs of the two radical units along with the classical spin polarization mechanism through the sigma-bonds of the metallocene unit. Lattice constants for both structures are as follows: 1 (M = Fe), C17H21FeN2O2, a = 7.170(1) A, b = 10.135(2) A, alpha = 10.683(2) A, alpha = 88.88(3), beta = 83.42(3), gamma = 79.75(3), triclinic, P1, Z = 2; 2 (M = Fe), C24H32FeN4O4, a = 11.848(3) A, b = 11.785(2) A, c = 17.728(4) A, beta = 106.25(2), monoclinic, P21/n, Z = 4.

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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 efficiency of the alkaloids quinine, cinchonine, cinchonidine and ephedrine, the aminoalcohols prolinol, and alaninol, as well as the aminoacids proline, and phenylalanine as catalysts for the enantioselective addition of diethylzinc to ferrocene carbaldehyde and benzaldehyde has been studied. The addition reactions proceeded with acceptable yields and low to moderate enantioselectivities. The side products ferrocenyl methanol and 1-ferrocenyl-1- propanone, observed during the additions to ferrocene carbaldehyde were isolated and characterized.

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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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Cyclic azomethine imines possessing a beta-aminocarbonyl motif are accessed from simple alkene and hydrazone starting materials. A thermal, concerted alkene aminocarbonylation pathway involving an imino-isocyanate intermediate is proposed and supported by DFT calculations. A notable feature of the process is the steric shielding present in the dipoles formed, which allows for facile purification of the products by chromatography or crystallization. In addition, a fluorenone-derived reagent is reported, which provides reactivity with several alkene classes and allows for mild derivatization of the dipoles into beta-aminoamides, beta-aminoesters, and beta-amino acids.

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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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Borane, as a DMS or a THF complex, can efficiently reduce a large range of ferrocenyl derivatives (aldehydes, ketones, ethers, acetals, carboxylic acids, esters,…) if they bear at least one oxygen at a carbon at the alpha position. On the contrary, similar molecules, which contain nitrogen instead of oxygen, do not react with borane.

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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 alpha-ferrocenylalkyl carbenium ions are formed from ferrocene and carbonyl compounds in strongly acidic media, in particular mixtures of fluorosulfuric acid and trichloroacetic acid.The alpha-ferrocenylalkyl carbenium ions are scavenged by nucleophiles or bases.The addition of nucleophiles produces the corresponding alpha-substituted ferrocenyl alkanes.Proton abstraction by base from the beta-position leads to the ferrocenylethene derivatives.Such electrophilic substitutions of ferrocene by carbonyl compounds, followed by suitable scavengeing of the alpha-ferrocenylalkyl carbenium ion, form the basis of one-pot syntheses of various ferrocene derivatives.

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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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MicroRNAs (MiRNAs) have been regarded as clinically important biomarkers and drug discovery targets. In this work, we reported a simple and ultrasensitive electrochemical method for miRNAs detection based on single enzyme amplification and electrochemical-chemical-chemical (ECC) redox cycling. Specifically, upon contact with the target miRNAs, the hairpin structure of biotinylated DNA immobilized on gold electrode was destroyed and the biotin group in DNA was forced away from the electrode surface, allowing for the coupling of streptavidin-conjugated alkaline phosphatase (SA-ALP). Then, ascorbic acid (AA, the enzymatic product of ALP) triggered the ECC redox cycling with ferrocene methanol (FcM) and tris(2-carboxyethyl)phosphine (TCEP) as the redox mediator and the chemical reducing reagent, respectively. The method was more sensitive than that with horseradish peroxidase (HRP) or glucose oxidase (GOx) triggered recycling since one ALP molecule captured by one target miRNA molecule promoted the production of thousands of AA. Analytical merits (e.g., detection limit, dynamic range, specificity, regeneration and reproducibility) were evaluated. The feasibility of the method for analysis of miRNA-21 in human serum has also been demonstrated.

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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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alpha-Ferrocenylcarbinols, readily obtained by direct condensation of aldehydes or ketones with ferrocene, react smoothly with mercaptosuccinic acid to give ferrocenylmethylthiosuccinic acids.The optically active dimethyl (R)-mercaptosuccinate provides a way for the resolution of tertiary alcohols.

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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 Equation Presented). A simple, highly efficient, and general strategy for the direct synthesis of amino-(N-alkyl)benzenesulfonamides has been accomplished via direct N-alkylation of aminobenzenesulfonamides bearing both different types of amino groups with alcohols as alkylating agents. Notably, this research exhibited the potential for the recognition of different types of amino groups in the N-alkylation of complex molecules with alcohols, facilitating the progress of the transition-metal-catalyzed “hydrogen autotransfer (or hydrogen-borrowing) process.”

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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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Novel ferrocenyl dendrimers with ferrocene as a surface group and with triazole as a bridging unit have been synthesised through click chemistry. The increasing numbers of triazole and ferrocenyl units at the antenna increase the light absorbing ability. The electrochemical behaviour changes with increasing ferrocenyl and triazole units.

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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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tetraphenylcyclobutadienecobalt(I) reacts with lithium tetrachloropalladate(II) in the presence of sodium acetate to give an ortho-palladated binuclear complex.The ?-bonded structure of the complex was confirmed by studies of the IR and 1H-NMR spectra and of the reactions with triphenylphosphine, thalium(I) acetylacetonate, and lithium aluminum deuteride.The reactions of the ?-bonded complex with carbon monoxide and olefins have been examined.

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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