Archives for Chemistry Experiments of Vinylferrocene

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The hexachloroplatinic acid-catalysed hydrosilylation of vinylferrocene by octahydrosilasesquioxane H8Si8O12 to the first organometallic monosubstituted octasilasesquioxane <(eta-C5H5)Fe(eta-C5H4CH2CH2)>– H7Si8O12 has been achieved.

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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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Alkyloxy- and aryloxy-functionalized titanocenes of type [Ti](Cl)(OR) (R = Me (2), CH2PPh2 (3), CH2Fc (4), C6H5 (5), C6H4-4-C{triple bond, long}N (6), C6H4-4-NO2 (7), C6H4-4-Me (8), C6H4-4-OMe (9), C6H4-4-C(O)Me (10), C6H4-4-CO2Me (11), C6H4-3-NO2 (12); [Ti] = (eta5-C5H4SiMe3)2Ti; Fc = (eta5-C5H4)(eta5-C5H5)Fe) were synthesized by the reaction of [Ti]Cl2 (1) with ROH in a 1:1 molar ratio and in presence of Et2NH. Diaryloxy-titanocenes (e.g., [Ti](OC6H4-4-NO2)2 (13)) are accessible, when the ratio of 1 and ROH is changed to 1:2. This synthesis methodology also allowed the preparation of dinuclear complexes of composition ([Ti](Cl))2(mu-OC6H4O) (14) and ([Ti](Cl)(mu-OC6H4-4))2 (15) by the reaction of 1 with hydroquinone or 1,1?-dihydroxybiphenyl in a 2:1 stoichiometry. Cyclic voltammetric studies show the characteristic [Ti(IV)/Ti(III)] reductions. It was found that the potentials of the alkyloxy titanocenes 2-4 do not differ, while for the aryloxy-titanocenes 5-15 the reduction potentials correlate linearly with the sigmap/m Hammett substituent constants showing a strong influence of the substituents on the electron density at titanium. The structures of titanocenes 4, 5, 9, and 11-13 in the solid state are reported. Typical for these organometallic sandwich compounds is a distorted tetrahedral coordination geometry around titanium with D1-Ti-D2 angles (D1, D2 = centroids of the cyclopentadienyl ligands) of ca. 130 . In comparison to FcCH2O-functionalized 4, for the aryloxy-titanocenes 5, 9, and 11-13 a significant larger Ti-O-C angle was found confirming electronic interactions between the titanium atom and the appropriate aryl group.

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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 SYMMETRIC 1,1′-disubstituted ferrocene- derived Schiff-bases have been prepared and used as ligands in the preparation of their novel Pd(II) and Pt(IV) metal chelates. The synthesized ligands and their metal chelates have been characterized by their physical, analytical and spectral data. These have also been used for screening against B. subtilis, S. aureus, E. coli, S. typhi (bacteria), C. albicans (yeast), A. niger and F. solani (fungi). The antimicrobial results indicated that the complexes prepared are more active than the ligand and have been found to be a novel class of organometallic-based antimicrobials.

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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 new complexes ; M=Fe or Ru and L*=(hydro)tris(3,5-dimethylpyrazolyl)borate, which contain a chelating metallocene ligand, have been prepared and characterised along with the related trimetallic complex <(Fe(eta5-C5H5)(eta5-C5H4CH2O)>2Mo(NO)L*>.Their electrochemical properties are reported, and the reduction potentials for the (4+) redox centre in the chelated species are 100 mV more anodic than for that in the trimetallic non-chelated complex.

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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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[3]Ferrocenophanone rac-8 was prepared by several non-Friedel-Crafts pathways starting from a Mannich-type coupling of 1,1?-diacetylferrocene followed by catalytic hydrogenation. Hydride abstraction from the resulting alpha-dimethylamino[3]ferrocenophane rac-14 with B(C6F 5)3 followed by hydrolysis gave the ketone rac-8. Several variants of the Sommelet reaction, using ethylglyoxylate, formaldehyde or hexamethylenetetramine (urotropine) as the “oxidizing” reagent gave the alpha-[3]ferrocenophanone 8 in good to excellent yield. Some variants of these reactions were also used for the preparation of the pure enantiomer (R)-8. The electrochemical behaviour of 8 has been investigated and compared with related derivatives. The Royal Society of Chemistry 2006.

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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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Cymantrenyl Schiff base compounds [(CO)3Mn{(eta5- C5H4)C(CH3)N-N(H)C(O)R}] (4-7) (R = C 6H4-OH, C5H4N-p, C6H 5, C5H4N-o) have been synthesized by room temperature reaction and their structural characterization was performed by single crystal X-ray diffraction studies. Room temperature reaction of mono- and di-acetyl ferrocene with salicyloyl and isonicotinyl hydrazides led to the formation of the some organometallic Schiff base compounds containing monosubstituted, disubstituted and unsymmetrically substituted ferrocenyl fragments, [(eta5-C5H5)Fe{(eta5- C5H4)C(CH3)N-N(H)C(O)-R}] (8, 9), [Fe{(eta5-C5H4)C(CH3)NN(H)C(O)R} 2] (10, 12) (R = C6H4-OH, C5H 4N), [{(eta5-C5H4)COCH 3}Fe{(eta5-C5H4)C(CH 3)NN(H)C(O)(C5H4N)}] (11) and [Fe{(eta5-C5H4)C(CH3)N-N(H)C(O) (C5H4N)}{(eta5-C5H 4)C(CH3)NN(H)C(O)C6H4-OH}] (13) respectively. Antibacterial studies and electrochemical analysis were carried out for some of the compounds. Molecular structure determination was performed for compounds 4, 5, 8 and 9 by single crystal X-ray diffraction technique.

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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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An improved synthesis of diethyl ferrocenylphosphonate using the tBuLi/tBuOK system at low temperature is reported and the structure of [FcPO3Et2]2 ·ZnCl2complex is described. The electrochemical behaviour of FcP(O)(OEt)2, 1,1?-fc[P(O)(OEt) 2]2, FcCH2P(O)(OEt)2, and their corresponding acids were compared. Each of them shows a reversible one-electron transfer reaction. Ferrocenylbisphosphonate is more difficult to oxidize than ferrocenylphosphonate due to the presence of two electron-withdrawing substituents. A methylene spacer between the ferrocenyl unit and the phosphonate group renders the compound easier to oxidize. The acids are easier to oxidize than the esters, and their salts, in which the phosphonate group behave as an electron-donating group, are even easier to oxidize than the ferrocene. The ferrocenylphosphonic acid may be, then, considered as a redox-active pH responsive molecule. Elsevier B.V. All rights reserved.

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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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Palladium-catalyzed enantioselective C(sp2)-H activation of ferrocenyl ketones is achieved through utilizing catalytic, inexpensive l-tert-leucine as a chiral transient directing group. The transformation allows rapid access to ferrocene scaffolds simultaneously possessing planar- and stereogenic central chirality, widely applied in the ferrocene-based chiral ligand families.

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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 forces between colloidal probes and several polymer films were measured by atomic force microscopy in the presence of a series of electrolyte solutions. For Nafion films using a negatively charged silica tip, a repulsive force was obtained at different concentrations of NaClO4. A similar result was obtained for an anion exchange membrane with a positively charged probe. Derjaguin-Landau-Verwey-Overbeek (DLVO) theory was employed to calculate the surface potential and hence, the surface charge. The surface charge density (a¿¼0.3I¼C/cm2) was independent of electrolyte concentration. The slope for plot of potential drop vs In[cs] was a¿¼0.020 V. A theoretical treatment based on GCS theory was employed to account for the above results. For a poly(vinylferrocene) (PVF) film, potential-dependent force curves were obtained, which were qualitatively different from that previously reported for an electronically conducting polymer film electrode.

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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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Title full: Synthesis and characterization of 1,1?-bis[(N-methyl-N-phenyl)aminomethyl(ethyl)]ferrocenes. Crystal structures of [Fe{(eta5-C5H4)-C(C6H 5){double bond, long}N-CH2C6H4CH3-4} 2] and 2[Fe{(eta5-C5H4)-CH2N (CH3)-C6H4OCH3-4}2] · 1/4H2O. Direct or catalytic condensation of diacylferrocenes (acyl = formyl, acetyl, and benzoyl) and anilines or benzylamines with titanium tetrachloride as a catalyst resulted in the corresponding diimines 1-3, respectively. Reduction of these imines with sodium borohydride or lithium aluminum hydride/aluminum chloride in THF yielded 1,1?-bis[(N-phenyl)aminomethyl(ethyl)]ferrocenes (4, 5) and 1,1?-bis[(N-benzyl)aminobenzyl]ferrocenes (6), respectively. Reductive methylation of 4-6 with aqueous formaldehyde, cyanoborohydride and acetic acid only afforded 1,1?-bis[(N-methyl-N-phenyl)aminomethyl(ethyl)]ferrocenes (7, 8). 1,1?-Bis[{(N-methyl-N-benzyl)amino}benzyl]ferrocenes (9) were not obtained, probably due to their debenzylation under the acidic conditions. The molecular structures of 3g and 7a were determined by single crystal X-ray analysis.

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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