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Stilbene analogues incorporating the Co(eta4-C 4Ph4)(eta5-C5H4-) end group

A number of organometallic stilbenes of the general type [Co(eta4-C4Ph4)(eta5-C 5H4CHCHR] are reported where R is C6H 4X-4 (X = H, OMe, Br, NO2), 1-naphthyl, 9-anthryl, 1-pyrenyl, (eta5-C5H4)Co(eta4- C4Ph4), and (eta5-C5H 4)Fe(eta5-C5H4Y) {Y = CHO, CHC(CN)2 and CHCHC5H4-eta5) Co(eta4-C4Ph4)}. They were prepared by Wittig or Horner-Wadsworth-Emmons reactions which yield both E and Z or only E products respectively. The isomers were separated and all compounds characterised by standard spectroscopic techniques as well as by X-ray diffraction methods in many cases. The electrochemistry of the stilbene analogues in dichloromethane solution is also reported. In most, the (eta5-C5H4)Co(eta4-C 4Ph4) functional group undergoes a reversible one-electron oxidation. For those molecules that also include (eta5-C 5H4)Fe(eta5-C5H4Y), this is preceded by the reversible oxidation of the ferrocenyl group. Spectroscopic and structural data suggests that for most compounds there is little electronic interaction between Co(eta4-C4Ph 4)(eta5-C5H4) and the R end groups which are effectively independent of one another. The only exceptions to this are Z and E-[Co(eta4-C4Ph4) (eta5-C5H4CHCHC6H 4NO2-4], and [Co(eta4-C4Ph 4)(eta5-C5H4CHCHC 5H4-eta5)Fe{eta5-C 5H4CHC(CN)2}] where the electronic spectra are respectively consistent with a significant Co(eta4-C 4Ph4)(eta5-C5H4)/ NO2 donor/acceptor interaction and a less significant Co(eta4-C4Ph4)(eta5-C 5H4)/C(CN)2 one. However, OTTLE studies show that in the electronic spectra of [Co(eta4-C4Ph 4)(eta5-C5H4CHCHR]+ there are low energy absorption bands (950-1800 nm) which are attributed to R ? Co(eta4-C4Ph4)(eta5- C5H4)+ or, when R is a ferrocenyl-base group, Co(eta4-C4Ph4)(eta5-C 5H4) ? (eta5-C5H 4)Fe(eta5-C5H4Y)+ charge transfer transitions. The ferrocenyl compounds undergo cis/trans isomerisation on the OTTLE experiment timescale.

Stilbene analogues incorporating the Co(eta4-C 4Ph4)(eta5-C5H4-) end group

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Application of 1271-48-3, Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps.In a article, 1271-48-3, molcular formula is C12H10FeO2, introducing its new discovery.

Electronic interactions in ferrocene- and ruthenocene-functionalized tetraazamacrcocyclic ligand complexes of FeII/III CoII, NiII, CeII and ZnII

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.

Electronic interactions in ferrocene- and ruthenocene-functionalized tetraazamacrcocyclic ligand complexes of FeII/III CoII, NiII, CeII and ZnII

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One of the major reasons for studying chemical kinetics is to use measurements of the macroscopic properties of a system, category: iron-catalyst, such as the rate of change in the concentration of reactants or products with time.In a article, mentioned the application of 1271-48-3, Name is 1,1′-Ferrocenedicarboxaldehyde, molecular formula is C12H10FeO2

Further solvent-free reactions of ferrocenylaldehydes: Synthesis of 1,1?-ferrocenyldiimines and ferrocenylacrylonitriles

Grinding of 1,1?-ferrocenedicarboxaldehyde with a 2.2 molar equivalent of an aromatic amine in a solvent-free environment provided excellent yields of 1,1?-ferrocenyldiimines. After mixing the aldehyde and amines, a gum or melt formed which eventually solidified to the product. An analytically pure sample of the product was obtained by cold recrystallization. Grinding of ferrocenecarboxaldehyde and 4-substituted phenylacetonitriles under solvent-free conditions provided good yields of the corresponding ferrocenylacrylonitriles. The yield in this reaction was very low when the substituent group para to the acetonitrile group was electron-donating.

Further solvent-free reactions of ferrocenylaldehydes: Synthesis of 1,1?-ferrocenyldiimines and ferrocenylacrylonitriles

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Synthesis of ferrocenylmethylidene and arylidene substituted camphane based compounds as potential anticancer agents

Herein is described the synthesis of (+)-camphor derivatives containing sulfonamide groups, ferrocenylmethylidene or arylidene moieties. The obtained derivatives were tested against seven human cancer cells lines, namely BV-173, K-256a, NB-4, A549, H1299, MCF-7, and MDA-MB231, and two normal human cell lines, HEK293 and HUVEC, in order to determine their activity against malignant cells. Some of them exhibit IC50 values below 10 muM in at least one of the cancer cell lines. Ferrocenylmethylidene ketone 16 can be outlined as the most potent and selective in the current study (IC50 for cancer cells-up to 4.0 muM; IC50 for HEK293 and HUVEC-68 and 69 muM, respectively). There is a clear trend showing that the presence of a conjugated ferrocenylmethylidene group is essential for the cytotoxicity, however different sulfonamide substituents and derivatization of the carbonyl group can modify the activity. Thus, this class of compounds could have good prospects for further structural optimisation.

Synthesis of ferrocenylmethylidene and arylidene substituted camphane based compounds as potential anticancer agents

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

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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Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Tricyclic quinazoline alkaloids conjugated to ferrocene: Synthesis, structure, and redox behavior of ferrocenylmethylene-substituted 7H-deoxyvasicinones

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.

Tricyclic quinazoline alkaloids conjugated to ferrocene: Synthesis, structure, and redox behavior of ferrocenylmethylene-substituted 7H-deoxyvasicinones

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Synthesis, X-ray structural determination and Moessbauer characterization of Schiff bases bearing ferrocene groups, their reduced analogues and related complexes

[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.

Synthesis, X-ray structural determination and Moessbauer characterization of Schiff bases bearing ferrocene groups, their reduced analogues and related complexes

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Ferrocenyl oligo(phenylene-vinylene) thiols for the construction of self-assembled monolayers

A short and efficient preparation of conjugated oligo(phenylene-ethylene) thiols bearing redox-active ferrocene moieties is described. While minimising the number of synthetic steps, the proposed strategy permits the development of sets of oligomers with varying chain length. The redox properties of the compounds in solution are determined. Preliminary studies of self-assembled monolayers (SAMs) on gold electrodes are discussed, and indicate that electron transfer through the SAMs is indeed rapid. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

Ferrocenyl oligo(phenylene-vinylene) thiols for the construction of self-assembled monolayers

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A chiral molecular bowl containing three ferrocenes: Synthesis and its efficiency in an optical resolution of 1,1?-bi-2-naphthol

Condensation reaction of 1,1?-ferrocenedicarboxaldehyde with (1R,2R)-1,2-diaminocydohexane affords a novel bowl-shaped macrocycle with a chiral concave cavity which exhibits a remarkable ability as a host material for the enantioselective enclathration of 1,1?-bi-2-naphthol.

A chiral molecular bowl containing three ferrocenes: Synthesis and its efficiency in an optical resolution of 1,1?-bi-2-naphthol

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Triad and cyclic diad compounds of [60]fullerene with metallocenes

Metallocene-bridged [60]fullerene triads and cyclised metallocene-[60] fullerene diads are formed via [3 + 2] cycloaddition reactions of [60]fullerene with metallocene dialdehyde and an amino acid. In the case of cyclic diads only one regioisomer is formed, as determined by UV-vis and NMR spectroscopic studies. These compounds have both electron donor (metallocene) and acceptor ([60]fullerene) components and give three electrochemically reversible one-electron reductions for each [60]fullerene moiety. For the ferrocene-containing compounds, an electrochemically reversible one-electron oxidation process is observed, with an irreversible oxidation observed for the ruthenocene analogues.

Triad and cyclic diad compounds of [60]fullerene with metallocenes

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