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The preparation and twin polymerization of the twin monomer Si(OCH2Fc)4 [Fc = Fe(eta5-C5H4)(eta5-C5H5)] (2) by the reaction of FcCH2OH (1) with SiCl4 in the presence of pyridine was explored. The electronic properties of 2 were investigated by cyclic voltammetry, square-wave voltammetry, and UV/Vis/near-IR spectroelectrochemistry, which showed a redox separation caused by electrostatic repulsion. Thermally induced condensation of 2 is characteristic, as evidenced by differential scanning calorimetry (DSC) and thermogravimetry coupled mass spectrometry (TG-MS). Upon heating 2 to 210 C, twin polymerization occurred and a hybrid material was formed that showed similarities with known systems derived from 2,2?-spirobi[4H-1,3,2-benzodioxasiline] (SBS), such as the nanopatterning of the formed silicon dioxide, which is characteristic for twin polymerization. Electron microscopy of this material revealed the absence of typical microstructuring found for other twin polymers, and hence, the herein presented system can be characterized as a borderline system if compared to known twin monomers such as SBS. The copolymerization of 2 and SBS afforded a hybrid material from which porous carbon or silica materials containing iron oxide nanoparticles could be obtained. The oxidation state of the incorporated particles was examined by Moessbauer experiments, which confirmed that only FeIII was incorporated within the porous carbon and silica materials, respectively. The preparation of iron oxide containing porous carbon capsules was achieved by applying a mixture of 2 and SBS to silicon dioxide spheres (d = 200 nm). After twin polymerization and carbonization, porous carbon capsules with incorporated iron oxide nanostructures were obtained. The straightforward preparation of iron-rich porous carbon and silica materials by twin polymerization of Si(OCH2Fc)4 [Fc = Fe(eta5-C5H4)(eta5-C5H5)] and 2,2?-spirobi[4H-1,3,2-benzodioxasiline] is reported; the electrochemical properties of Si(OCH2Fc)4 are discussed.

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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

 

The important role of Vinylferrocene

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Four first- and second-generation heterometallic ferrocenyl derived p-cymene-Ru(II) metallodendrimers, of general formula [DAB-PPI{(kappa6-p-cymene)Ru((C7H5NO)-2-N,O)PTA(5-ferrocenylvinyl)}n][PF6]n and [DAB-PPI{(kappa6-p-cymene)Ru((C6H5N2)-2-N,N)Cl(5-ferrocenylvinyl)}n][PF6]n (where n = 4 (G1), 8 (G2), DAB = 1,4-diaminobutane, PPI = poly(propyleneimine), PTA = 1,3,5-triaza-7-phosphatricyclo[3.3.1.1]decane) have been synthesized. All complexes have been characterized using analytical (i.e., HR-ESI mass spectrometry, HPLC, elemental analysis, and cyclic voltammetry) and spectroscopic (i.e., 1H and 13C{1H} NMR and infrared) methods. Electrochemical studies reveal that the N,O-p-cymene-Ru(II)-PTA complexes result in two irreversible redox processes (oxidation of the Fe(II) and Ru(II) centers), while the N,N-p-cymene-Ru(II) complexes display one reversible wave (Fe(II)/Fe(III) couple). Heterometallic model complexes have been prepared, and for one of the complexes, its molecular structure has been determined by single-crystal X-ray crystallography. In vitro antiproliferation activity of the dendritic ligands and their complexes were evaluated against A2780 and A2780cisR human ovarian cancer lines, the SISO human cervix cancer line, the LCLC-103H human lung cancer line, and the 5637 human bladder cancer line. Nine of the twelve compounds slowed the growth of the ovarian cancer cell lines by more than 50% at equi-iron concentrations of 5 muM.

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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

 

Discover the magic of the 1,1′-Ferrocenedicarboxaldehyde

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The synthesis and characterization of a novel redox molecular receptor is reported. This chemosensor is structured on a ferrocene fragment whose cyclopentadienyl moieties have been connected to distinct and complementary zinc porphyrin and alkylammonium binding sites, enabling multipoint recognition and detection of anionic species. Cumulative effects of multiple anchoring points on this ammonium-ferrocene-metalloporphyrin chemosensor allowed the unprecedented ferrocene-based voltammetric sensing of halide anions.

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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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Ruthenium nanoparticles (NPs) supported on N-doped carbon (Ru/N?C) were prepared by the pyrolysis of cis-Ru(phen)2Cl2 loaded onto carbon powder (VULCAN XC72R) at 800 C. Ru/N?C NPs (0.2 mol% Ru) selectively catalyzed either acceptorless dehydrogenation coupling (ADC) or auto-transfer-hydrogen (ATH) reactions of amines with alcohols to imines and secondary amines. Such selectivity could be controlled by the choice of alkali metal ion associated with the base. Under similar catalytic conditions, the ADC cross-coupling of diamines with primary alcohols or diols afforded the corresponding benzimidazoles and quinoxalines in good to excellent yields. This catalytic system displayed good activity, recyclability, and wide applicability to a diverse range of substrates.

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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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2-Vinylpyridines undergo regioselective beta-alkylation with alkenes in the presence of a rhodium(I) complex as a catalyst to give products resulting from an anti-Markownikoff reaction. These results show the feasibility of alkylation of an alkenic position as a result of C-H bond activation. 2-(Prop-1-en-2-yl)pyridine 1 and 1-phenyl-1-(2-pyridyl)ethylene 15 react with linear terminal alkenes to give the corresponding alkylated products in high yields. Cyclic alkenes, allyl alcohol, but-3-en-1-ol and methyl vinyl ketone, however, fail to react with 1. Pent-2-ene gives the linear alkylated product in low yield. 6-Methyl-2-vinylpyridine 24 and 2-vinylpyridine 32 give the alkylated products in low yield together with their dimeric products. The alkenic C-H bond of 2-(cyclohex-1-enyl)pyridine 36 has been regioselectively alkylated. 2-(Cyclohex-1-enyl)pyridine 36 with alkenes in the presence of the RhI catalyst undergoes regiospecific alkylation at the alkenic position.

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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

 

Properties and Exciting Facts About Ferrocenemethanol

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With the emerging interest in layered transition metal dichalcogenides (TMDs), MoS2 has occupied a unique place in recent times as graphene (GR) analog. Development of novel state of the art electrochemical approaches at MoS2 modified working surfaces is an upcoming field and holds great promise for design and development of next generation sensing devices. Large available surface area, high biocompatibility and structural versatility of 2D/3D MoS2 nanostructures have produced numerous hybrid sensors and biosensors which have demonstrated their prominent role in biological, environmental, pharmaceutical, chemical, industrial and food analysis. A comprehensive and critical detail of recent advancements of MoS2 based sensors for real time applications have been presented in the present review. Overall conclusion related to sensing performances of MoS2 nanostructures and future needs to further exploit the unusual properties of mono and few layer of other TMDs for developing advance recognition systems have been concluded at the end.

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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 zinc complex [PhP(S)(NMeNH2)2]ZnCl2 (2), cleanly obtained by reaction of the phosphodihydrazide PhP(S)(NMeNH2)2 (1) with ZnCl2, is a good reagent in producing new polymetallic compounds by condensation reaction with aldehydes. The reaction of 2 with terephthalaldehyde (3) in a 2/1 or 1/1 stoichiometry leads selectively to the acyclic zinc compound [C6H4-1,4-(CH=NNMePhP(S)NMeNH2)2][ZnCl2]2 (6) or to the macrocyclic zinc complex [PhP(S)C6H4-1,4-(CH=NNMe)2]2[ZnCl2]2 (7). Reaction of compound 2 with 2 equiv of ferrocenecarbaldehyde affords the zinc-iron phosphodihydrazone complex [PhP(S)(NMeN=CHC5H4FeCp)2]ZnCl2 (8) whose structure has beendetermined by X-ray crystallography. Crystal data: triclinic P1-, with a = 12.798(1) A, b = 14.639(2) A, c = 11.744(2) A, alpha =111.74(1)°, beta = 115.92(1)°, gamma = 68.36(1)°, V = 1780.9 A**3, Z = 2; R = 0.037, Rw = 0.044 for 3345 observations and 448 variable parameters. In this neutral trimetallic complex, the Zn(II) center adopts a pseudotetrahedral geometry. This structure is characterized by a five-membered ring with the Zn(II) bonded to the S atom and to one of the N atoms of the phosphodihydrazone ligand PhP(S)(NMeN=CHC5H4FeCp)2 (9). Variable-temperature NMR investigations of 8 show that 9 can act as a hemilabile ligand toward ZnCl2 through an exchange process between the two hydrazone arms in solution. Electrochemical study ofcomplex 8, when compared to the ferrocenyl ligand 9, shows that ZnCl2 complexation induces a shift of 80 mV toward a more anodic potential. Reaction of 2 with the ferrocene-1,1′-dicarbaldehyde also produces the bisferrocenyl dizinc macrocycle [Fe(C5H4CH=NNMePhP(S)NMeN=CHC5H4)2Fe][ZnCl2]2 (10).

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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 compounds and metal complexes containing both ferrocene and sulfur-based ligands have been prepared and their properties investigated.The reaction of 2 with (chlorometyl)ferrocene led to the compound 4,5-bis(ferrocenylmethylsulfanyl)-1,3-dithiole-2-thione.Similarly, the reaction of the salt Cs2, led to the ketone analogue, 4,5-bis(ferrocenylmethylsulfanyl)-1,3-dithiole-2-one.The latter has been used to prepare a monoanionic tetraferrocenyl nickel dithiolene complex which shows an intense NIR absorption at 1250 nm recorded in CH2Cl2.Intermolecular coupling of the thione gave the novel tetra(ferrocenylmethylsulfanyl)tetrathiafulvalene electrochemical investigations of which revealed characteristic ttf and ferrocenyl redox processes.The single-crystal structure of this compound has also been determined.

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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 series of new conjugated bimetallic ferrocenyl 1,1?-bis- substituted compounds of the type (E)-[CpFe(eta6-p-RC 6H4)NHN=CH(eta5-C5H 4)Fe(eta5-C5H4)-CH=CHC 6H4-p-R?]+PF6- (Cp = eta5-C5H5; R, R? = H, NO 2, 11; Me, NO2, 12; MeO, NO2, 13; Cl, NO 2, 14; Me, CN, 15; Me, Me, 16), with end-capped (E)-ethenylaryl and [CpFe(arylhydrazone)]+ substituents, have been prepared by the condensation reaction of 1,1?-(p-R?-arylethenyl) ferrocenecarboxaldehyde (R? = Me, 4; NO2, 5; CN, 6) with the organometallic hydrazine precursors [CpFe(eta6-p-RC 6H4NHNH2)]+PF6 – (R = H, 7; Me, 8; MeO, 9; Cl, 10). In the trimetallic series, {[CpFe(eta6-p-RC6H4)NHN=CH(eta 5-C5H4)]2Fe}2+[PF 6-]2 (R = H, 17; Me, 18; MeO, 19, Cl, 20), which results from the condensation of two equivalents of the same organometallic hydrazine precursor (7-10) with 1,1?- ferrocenedicarboxaldehyde, the ferrocenediyl core symmetrically links two cationic mixed-sandwich units. These ten hydrazones (11-20) were stereoselectively obtained as their trans isomers about the N=C double bond. All the new compounds were thoroughly characterized by a combination of elemental analysis, spectroscopic techniques (1H NMR, IR and UV-Vis) and electrochemical studies in order to prove electronic interaction between the donating and accepting units through the pi-conjugated system. A representative example of each series has also been characterized by single crystal X-ray diffraction analysis. The bimetallic complex 16+ adopts an anti conformation with the two iron atoms on opposite faces of the dinucleating hydrazonato ligand, whereas the trinuclear complex 192+ adopts a syn conformation with an Fe-Fe-Fe angle of 180. Other salient features of these structures are the long Fe-Cipso bond distances and the slight cyclohexadienyl character at the coordinated C6 ring, with a folding angle of 7.4 and 7.0 for 16+ and 19 2+, respectively.

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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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Bicontinuous microemulsions (BMEs, Winsor III), also called middle-phase microemulsions, are low-viscosity, isotropic, thermodynamically stable, and spontaneously formed mixtures of water, oil, and surfactants. They are unique solution media for electrochemistry. Here, we introduce the recent progress in the electrochemistry of BMEs from their fundamental aspects to their practical applications. Electrochemistry using BMEs has two irreplaceable properties: the coexistence of hydrophilic and lipophilic species with high self-diffusion coefficients; and the dynamic deformation of structures at an oil/water/electrode ternary interface, which is easily changed according to the property of the electrode surface. Electrochemical contact with the micro-saline and oil phases in a BME is alternately or simultaneously achieved by controlling the hydrophilicity and lipophilicity of the electrode surfaces. The selective electrochemical analysis of hydrophilic and lipophilic antioxidants in liquid foods without extraction demonstrated as the use of the unique ternary solution structures of BME on solid surfaces.

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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