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Lithioferrocene, 1,1′-dilithioferrocene, lithioruthenocene and 1,1′-dilithioruthenocene all react with N,N-dimethylformamide in diethyl ether to produce the respective aldehydes.The lithiation of the two metallocenes can be steered to maximize the formation of only one of the two aldehydes by choosing either n-butyllithium in the presence of tetramethylethylenediamine (TMEDA) or t-butyllithium (tBuLi) as the metallating reagent: ferrocene mono-aldehydes or 1,1′-dialdehydes are formed with good yields (91percent and 85percent respectively, based on ferrocene), lower yields (50percent) of ruthenocene-1,1′-dialdehyde were obtained under the standard conditions, because the 1,3,1′-trialdehyde also formed in significant (19percent) amounts.Monolithiation by nBuLi and the formation of the ruthenocene monoaldehyde (yield, 66percent) are favoured when TMEDA is used in only catalytic amounts; lithiation of ruthenocene by tBuLi selectively leads to monolithioruthenocene and the mono-aldehyde (yield, 91percent).The products are easily purified by column chromatography.The simplicity and the high yield of these reactions make them much more desirable than the previously known multistep procedures.

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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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Extensive TDDFT calculations with various combinations of functionals are carried out to compute low-lying excited states of ferrocene. The combined functional and basis set approach TD-PBE0/6-311++G(d,p) is found to be well-behaved in the calculation of excited states. This choice of functional/basis set can give correct ground-state geometries, excitation energies, absorption spectra, and correct symmetry sequence of low level unoccupied molecular orbitals. This method is applied to the calculation of excitation energies of bis(benzene)chromium and four derivatives of ferrocene and the results are accurate within 0.3 eV. The current study implies that the combination TD-PBE0/6-311++G(d,p) can be used to compute excited state properties of other transition metal complexes.

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The solubility of acetylferrocene and diacetylferrocene in mixtures of water with dimethylsulfoxide was determined as a function of temperature and mole fraction of the organic component. Changes in the thermodynamic functions in the transfer of acetylferrocene and diacetylferrocene from water into a mixed solvent were estimated and analyzed.

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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 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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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 effects of a direct connection between ferrocene and porphyrin units have been thoroughly investigated by electrochemical and spectroscopic methods. These data not only reveal that substitution of the porphyrin macrocycle by one, two, three or four ferrocenyl groups strongly affects the electronic properties of the porphyrin and ferrocenyl moieties, they also clearly demonstrate that the metallocene centres are “connected” through the porphyrin-based electronic network. The dynamic properties of selected ferrocene-porphyrin conjugates have been investigated by VT NMR and metadynamic calculations. 1,3-Dithiolanyl protecting groups have been introduced on the upper rings of the ferrocene fragments to allow a straightforward and easy access to redox active picket-fence porphyrins. X-ray diffraction analyses of the zinc(ii) 5-[1?-[2-(1,3-dithiolanyl)]ferrocenyl]-10,15,20-tri(p-tolyl)porphyrin and 5,15-bis[1?-[2-(1,3-dithiolanyl)]ferrocenyl]-10,20-bis(p-tolyl)porphyrin complexes reveal the existence of S-Zn bonds involved in supramolecular arrays. The solid state analysis of the trans-5,15-di-(1?-(formyl)ferrocenyl)-10, 20-di-(p-tolyl)-porphyrinatozinc(ii) complex, obtained by deprotection of the dithiolane substituted analog, is conversely found in the crystal lattice as a monomer exhibiting a hexacoordinated zinc metal centre. The Royal Society of Chemistry 2013.

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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+1], [1+2], [2+1] or [3+1] acyclic and [1+1] or [2+2] cyclic Schiff bases (LALS), containing ferrocene moieties, have been prepared by reaction of formyl- or 1,1?-diformylferrocene and the appropriate amines. Formyl- and 1,1-diformylferrocene form respectively the acyclic [2+1] LW and [2+2]n LZ compounds by reaction with 1,4-diaminomethylbenzene. Similar compounds (LTLV) have been obtained by condensation of aminomethylferrocene and 2,6-diformylpyridine, 2,6-diformyl-4-chlorophenol and 3-methoxy-2-hydroxybenzaldehyde. By reduction of these compounds with NaBH4 the corresponding ferrocene-amine derivatives (L?) have been synthesized. All these compounds have been characterized by physico-chemical measurements (IR, NMR, Moessbauer spectroscopy and FAB mass spectrometry) and LH, derived by the condensation of ferrocene-aldehyde and 1,5-diamino-3-oxa-pentane, also by an X-ray structural determination. The X-ray analysis of crystals of LH, grown from a diethyl ether solution, shows that two independent molecules are present in the asymmetric unit; these two molecules are chemically equivalent with the ferrocenyl groups in the eclipsed form. The coordination ability of these compounds towards d metal ions as copper(II), nickel(II), platinum(II) and rhodium(III) was investigated; while the Schiff bases (L) may suffer hydrolysis, their reduced analogues (L?) form stable, well-defined complexes of the type M(L?)(Cl)n (n=2, 3). The Moessbauer spectra of the prepared compounds show signals with delta at 0.44 and DeltaEQ 2.30 mm s-1 for the Schiff bases LALS and 0.52 and 2.40 mm s-1 for the reduced analogues and hence may be diagnostic of the presence of Fe-CH=N- or Fe-CH2-NH- groups. The signals with delta at 0.51-0.55 and DeltaEQ at 2.34-2.38 mm s-1 for the Schiff bases LTLV, having Fe-CH2-N=CH groups, resemble those of the reduced analogues.

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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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Ferrocene containing N-tosyl hydrazones as selective and sensitive optical and electrochemical chemosensors were synthesized and characterized by 1H NMR, 13C NMR, ESI-MS and X-ray analysis. The cation and anion binding studies were carried out using various techniques including electrochemistry, UV?vis and 1H NMR spectroscopy. Chemosensors 2a and 2b have shown excellent selective recognition toward Hg2+, Cu2+ and F? through optical and electrochemical signals. The color of 2a and 2b in solution changed visibly from pale yellow to red upon addition of Hg2+ion, while the color of solution changed from pale yellow to yellow green upon addition of Cu2+, which can be easily detected by the naked eye.

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In the present manuscript, the electrochemical behavior of cytochrome c (cyt-c) immobilized onto a phenolic terminated self assembled monolayer (SAM) on a gold electrode is investigated using cyclic voltammetry (CV) and scanning electrochemical microscopy (SECM). The tunneling electron transfer (ET) rate constant between the immobilized protein and the underlying electrode surface, and also the bimolecular ET rate constant between the immobilized protein and a probe has been obtained using approach curves that were obtained by SECM. The approach curves were recorded at different substrate overpotentials in the presence of various concentrations of ferrocyanide as a probe and various surface concentrations of cyt-c; then the standard tunneling ET and bimolecular rate constants are obtained as 3.4 ± 0.3 s-1 and (2.0 ± 0.5) × 107 cm3 mol-1 s-1, respectively.

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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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Copper-catalyzed stereoconvergent allylation of chiral sp3-hybridized carbon nucleophiles with a racemic mixture of acyclic secondary allylic phosphates is reported. In the presence of a copper-catalyst complexed with chiral BenzP* ligand, tandem coupling reaction of vinyl arenes, bis(pinacolato)diboron, and racemic allylic phosphates provided beta-chiral alkylboronates possessing (E)-alkenyl moiety through a direct stereoconvergent allylic coupling with concomitant generation of a C(sp3)-stereogenic center. A range of vinyl (hetero)arenes and secondary allylic phosphates bearing 1, 2, 3 alkyl and phenyl alpha-substituents were suitable for the reaction, forming products with high enantioselectivities up to 95 % ee. Density functional theory calculations were conducted in detail to elucidate the origin of the observed regioselectivity of borylcupration and stereoconvergent (E)-olefin formation from racemic allylic phosphates.

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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