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The keto-phosphines (L1), <(Ph2PCH2C(O)(eta5-C5H4))2Fe> (L2) and <(Ph2PCH2C(O)(eta5-C5H4)C(O)CH3)> (L3) were respectively prepared by the reaction of Ph2PCl with the lithium enolates derived from acetylferrocene for L1, and 1,1′-bis(acetyl)ferrocene for L2 and L3.Ligand L1 crystallizes in the space group P1 with a 8.526(2), b 10.915(3), c 12.822(3) Angstroem, alpha 63.75(2), beta 69.04(2), gamma 70.77(2) deg, V 978.4 Angstroem3 and Z 2.The structure was solved and refined to R=0.034 and RW=0.042.The C5-rings are eclipsed (3.2 deg) and the plane of the keto group forms a dihedral angle of 13.1 deg with the C5H4 plane.In the complexes cis- and trans- (cis-1 and trans-1), <(o-C6H4CH2NMe2)PdClL1> (2), cis- (3), and (4) the phosphine ligand(s) behave as P-monodentate(s).The structure of trans-1 has been determined by X-ray diffraction at -145 deg C.The complex crystallizes in the monoclinic space group P21/c with a 10.622(7), b 12.647(7), c 15.59(1) Angstroem, beta 103.20(6) deg, V 2039 Angstroem3 and Z=2.The structure was solved and refined to R=0.037 and RW=0.053.The palladium atom lies on a centre of symmetry and the Pd-P and Pd-Cl bond lengths are respectively 2.314(1) and 2.287(1) Angstroem.The C5-rings of each ligand are slightly staggered (10.5 deg) and, as for L1, each keto group is almost parallel to the C5H4 plane (dihedral angle 8.9 deg).For the complex BF4, NMR and IR solution spectroscopy has shown that there is a dynamic exchange between chelating and P-monodentate L1.The possibility of using L2 as a binucleating ligand was demonstrated by the preparation of the trinuclear complex <((C10H8N)PdCl)2(mu-L2-P,P')> (6).The enolato complexes cis- (M=Pd (7), M=Pt (8)), and <(o-C6H4CH2NMe2)Pd(Ph2PCH=C(O)(eta5-C5H4)Fe(eta5-C5H5))> (9) were prepared in high yield by the reaction of NaH with complexes 1, 3, and 2, respectively.Complex 9 reacts with dimethylacetylenedicarboxylate to yield the alkenyl complex <(o-C6H4CH2NMe2)Pd(Ph2PCH(MeO2CC=CCO2Me))> (10), resulting from carbon-carbon coupling between the P bound enolate-carbon atom and the alkyne.All the complexes were characterized by elemental analysis, and 1H and 31P(1H) NMR and IR spectroscopy.

beta-Keto phosphines derived from ferrocene. Syntheses and structures of (L1) and trans-

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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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Barbier-type gamma-regiospecific allylation of formylferrocene (1) with allyl bromides in the presence of stannous chloride dihydrate and catalytic cupric chloride in dichloromethane-water (1:1) afforded corresponding ferrocenyl dienes FcCHC(R1)C(R2)CH2 (3-6). On the other hand, similar reactions of 1,1?-bis-formylferrocene (2) yielded oxa-bridged [3]-ferrocenophanes having allyl pendants Fc[CH2C(R2)CH(R1)CH-mu(O)-CHCH (R1)C(R2)CH2] (8-11). The latter appear to result from the dehydration of intermediate homoallylic alcohols. Dehydration could be arrested in case of reaction of 1 and 2 with 1-bromo-3-methyl-but-2-ene, which results in the formation of homoallylic alcohols FcCH(OH)C(Me2)CHCH2 (7) and Fc[CH(OH)C(Me2)CHCH2]2 (12), respectively. All the reactions completely fail in absence of water.

Synthesis of ferrocenes with ene-terminus via water-promoted Barbier-like carbonyl allylation using bimetallic copper(II)/tin(II) reagent

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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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Synthesis of environmentally-sensitive, and therefore smart hydrogels of micro- and nanosize allowed substantial shortening of time of response of these gels to a change in environmental conditions. This made the hydrogels much more attractive and opened new possibilities of their applications. In this paper we present recent developments in ways of construction of micro- and nanogels, their adaptation to particular needs and possibilities of use. The focus was given to individual, spherical particles and very thin layers of gels on solid supports, including electrodes.

Recent developments in design and functionalization of micro- and nanostructural environmentally-sensitive hydrogels based on N-isopropylacrylamide

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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 discontinuous temperature dependence of Moessbauer recoil-free fraction observed in diethylferrocene, reflects the transition from the glass state to the super-cooled liquid state followed by crystallization on heating the sample which was prepared by cooling quickly the liquid sample with liquid nitrogen.On cooling the crystallized diethylferrocene, the temperature dependence was similar to that found monoethylferrocene.

MOESSBAUER SPECTROSCOPIC STUDIES ON THE GLASS STATE IN DIETYLFERROCENE

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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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We have synthesized a series of novel SERMs bearing a ferrocenyl unit based on a three-dimensional oxabicyclo[2.2.1]heptene core scaffold. These compounds displayed high receptor binding affinities as well as ERalpha or ERbeta selectivity. In cell proliferation assays, we found that these ligands were cytotoxic at micromolar concentrations in both ER-positive and ER-negative breast cancer cells. On further examination, we found that the antiproliferative effects of compounds 9b, 10h and 11b on MCF-7 cells line does not arise from antiestrogenicity, but rather proceeds through a cytotoxic pathway. Possible mechanisms for the unique activities of these ligands were also investigated by molecular modeling. These new ligands could act as scaffolds for the development of novel anti-breast cancer agents. The Royal Society of Chemistry 2012.

Discovery of novel SERMs with a ferrocenyl entity based on the oxabicyclo[2.2.1]heptene scaffold and evaluation of their antiproliferative effects in breast cancer cells

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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 heterogeneous catalysis, catalysts provide a surface to which reactants bind in a process of adsorption. In homogeneous catalysis, catalysts are in the same phase as the reactants. Recommanded Product: Ferrocenemethanol. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 1273-86-5, Name is Ferrocenemethanol

Abstract?: Results of the studies in the adsorption properties of ??6, ??7, ??8 cucurbituril complexes with inorganic cations (Na+, K+, Cs+), cation of 3,3′-diethyltiocarbocyanine iodide organic dye and neutral organic compounds: adamantanol-1 and ferrocene at the electrode/solution interfaces are summarized. Effects of different factors on the adsorption behavior of the studied supramolecular complexes are analyzed.

The Effect of Different Factors on the Adsorption of Cucurbituril Complexes at Electrode/Solution Interfaces

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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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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.

A simple synthesis of metallocene aldehydes from lithiometallocenes and N,N-dimethylformamide: ferrocene and ruthenocene aldehydes and 1,1′-dialdehydes

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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 conjugates of ferrocene with uracil, 5-fluorouracil, tegafur, or acyclovir are reported. Their synthesis involved (i) the azide-alkyne 1,3-dipolar cycloaddition or (ii) the formation of the ester linkage. For the first time, we present an in-depth insight into the supramolecular interactions between beta-cyclodextrin and ferrocene-nucleobase derivatives. Spectroscopic and voltammetric analyses performed within this work suggested that the ferrocene or adamantane unit of the conjugates interacted with the beta-cyclodextrin’s inner cavity. The methods applied for the supramolecular studies included 1H-1H ROESY NMR, 1H NMR titration, Fourier-transform infrared spectroscopy, cyclic voltammetry, fluorescence spectra titration, and 1H DOSY NMR. 1H DOSY NMR was also employed to evaluate the apparent binding constants for all the complexes. The ferrocene-acyclovir conjugate Fc-5 featured the highest apparent binding constant value among all the complexes tested.

Supramolecular Interactions between beta-Cyclodextrin and the Nucleobase Derivatives of Ferrocene

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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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A new method for the hydrosilylation of alkynes controlled by a platinum catalyst with a monophosphine ligand (called TBSO-MOP) was explored. The platinum-catalyzed multicomponent and sequential silylation reaction involving alkynes, alcohols, and dihydrosilanes resulted in the highly stereoselective and high-yielding construction of functional (E)-vinylsilyl ethers. Moreover, the one-pot bis-hydrosilylation of terminal alkynes with dihydrosilanes was also achieved with the same platinum catalyst system.

Platinum-Catalyzed Multicomponent Alcoholysis/Hydrosilylation and Bis-hydrosilylation of Alkynes with Dihydrosilanes

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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 diiron bridging vinyliminium complexes [Fe2{mu- eta1:eta3-C=N(Me)2C(R?)=C(R?)} (mu-CO)(CO)(Cp)2][SO3CF3] (R? = H, R? = SiMe3, 3a; R? = H, R? = Tol =4-MeC 6H4, 3b; R? = Me, R? = Me, 3c; R? = SPh, R? = Me, 3d; R? = H, R? = Fc = [Fe(C5H 4)(Cp)], 6e) react with propargyl alcohol (HC?CCH 2OH), in refluxing toluene, affording the polysubstituted ferrocenes as mixtures of two isomeric forms: [1-NMe2-2-R?-3-R?-5- CH2OCH2C?CH-Fc] (R? = H, R? = SiMe 3, 6a; R? = H, R? = Tol, 6b; R? = Me, R? = Me, 6c; R? = SPh, R? = Me, 6d, R? = H, R? = Fc, 6e) and [1-NMe2-2-R?-3-R?-4-CH2OCH2C? CH-Fc] (R? = H, R? = SiMe3, 7a; R? = H, R? = Tol, 7b; R? = Me, R? = Me, 7c; R? = SPh, R? = Me, 7d) in overall yields of about 55-65%. Formation of the functionalized cyclopentadienyl in the ferrocene products takes place through the assembly of two propargyl units with the bridging vinyliminium ligand: one alkynol is incorporated by a [3 + 2] cycloaddition with the bridging C3 ligand; a second alkynol unit gives rise to a pendant chain through -OH substitution. Investigations show that the substitution step is catalyzed by the parent diiron complex itself or by a mononuclear iron fragment (likely the Fp+ complex). The pendant propargyl chain has been exploited to connect the ferrocene to other molecular fragments: in particular, the reaction of 6a with 4-biphenyl azide, by copper-catalyzed azide-alkyne cycloaddition (CuAAC), leads to the formation of the triazole-functionalized ferrocene [1-NMe 2-2-CH2OCH2-N3(C6H 4Ph)C2H-4-SiMe3-Fc] (12). Moreover, 6a reacts with Co2(CO)8, affording the complex [Co 2{mu-eta2-HC?CR}(CO)6] (13), (HC?CR = 6a), where the alkyne adopts a eta2 coordination to a dicobalt hexacarbonyl fragment. The molecular structure of 7a has been determined by X-ray diffraction studies.

Ferrocenes containing a pendant propargylic chain obtained via addition of propargyl alcohol to mu-vinyliminium ligands in diiron complexes

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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