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Ferrocenylimidazolium salts with methylene and phenyl groups bridging the ferrocenyl and alkylimidazolium moieties were synthesized and characterized by spectroscopic and analytical methods. Crystal structures of two new compounds are also reported. Cyclic voltammetry was used to analyze the influence of the two bridging groups or spacers on electrochemical properties of the salts relative to the shifts in the formal electrode or peak potentials (E0 or E1/2) of the ferrocene/ferrocenium redox couple. Results from this study showed that all the salts exhibited higher electrode potentials relative to ferrocene, which is due to the electron-withdrawing effect of the imidazolium ion on the ferrocenyl moiety. Application of the salts as catalysts in transfer hydrogenation of ketones resulted in high conversion of saturated ketones to corresponding alcohols and turnover numbers as high as 1880. The catalysts were chemoselective towards reduction of the C=C bonds of conjugated 3-penten-2-one and 4-hexen-3-one to yield saturated ketones, while unconjugated 5-hexen-2-one was hydrogenated to an unsaturated alcohol. Copyright

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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 redox switching of poly(vinylferrocene) (PVF) films was investigated using the electrochemical quartz crystal microbalance in conjunction with cyclic voltammetry (at different voltage scan rates) and reverse potential steps. The mechanism of the redox process was determined using PVF films supported on Au electrodes and exposed to aqueous bathing solutions of 0.1 M sodium hexafluorophosphate. PVF electro-oxidation proceeds via coupled oxidation of uncharged ferrocene sites and entry of counterion and is followed by the entry of water into the film. Structural changes within the polymer may also accompany the latter two steps. Any of these three steps may be the slowest for particular redox conditions. The controlling kinetic step depends on the film’s instantaneous water content, its instantaneous oxidation state, the electrochemical control function, the direction of redox switching, and the associated time scale of the experiment. We describe a new general quantitative approach based upon comparison of the instantaneous fluxes of solvent (water) and counterion during the redox cycle to characterize the rate-controlling process as a function of the extent of film oxidation. This new methodology has the capability to resolve time scale- and potential- (charge-) dependent mechanistic shifts and film relaxation phenomena as they are reflected through the ratio of fluxes of solvent and counterions.

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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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Condensation of diacetylferrocene with cyclohexanone, alkyl- or phenyl-cyclohexanones and cycloheptanone carried out in DMSO in the presence of KOH afforded 3-spiro<5>ferrocenophane-1,5-diones.Cyclopentanone and cyclooctanone failed to give the spiroferrocenophanediones.The mechanism of the reaction, its limitations and side products are discussed.Detailed analysis of the 1H NMR and 13C NMR spectra revealed an influence of the cyclohexane ring substituents on the flexibility of the spiroferrocenophanedione bridge.Fragmentation of the product molecules upon electron impact is also described.

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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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2,3-Diferrocenyl-1-methylthiocyclopropenylium iodide reacts with water, metal alkoxides, phenolates and with alcohols in the presence of Et3N to give E-1,2-diferrocenyl-3-methylthioprop-2-enone or its ketals. Their structures were established based on data from 1H and 13C NMR spectroscopy and X-ray diffraction analysis. The mechanistic aspects of these reactions are discussed. Electrochemical properties of 8 and 13b have been studied. The compounds present two oxidation processes (I-II), attributed to the oxidations of the ferrocenes groups, E0?(I), E0?(II), DeltaE0?(II-I) and comproportionation constant Kcom are reported.

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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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Highly enantioselective iron-catalyzed C?H alkylations by inner-sphere C?H activation were accomplished with ample scope. High levels of enantiocontrol proved viable through a novel ligand design that exploits a remote meta-substitution on N-heterocyclic carbenes within a facile ligand-to-ligand H-transfer C?H cleavage.

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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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Glassy carbon (GC) and Au electrodes were modified with aminophenyl films by electroreduction of the corresponding diazonium salt. Aminophenyl films were diazotised using both aqueous and non-aqueous conditions, to generate film-based phenyldiazonium ions. The stabilities of the diazonium terminated films, to exposure to air and in acidic solution, were investigated by cyclic voltammetry (CV). For films of the same thickness, those grafted to Au substrates are more stable than those grafted to GC.

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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 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.

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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 synthesis and characterization of pyrazole derivatives of general formula [C6H4-4-R-1-{(3,5-Me2-C3N 2)-CH2-(eta5-C5H4) Fe(eta5-C5H5)}] [R = OMe (1a) or H (1b)] with a ferrocenylmethyl substituent are described.The study of the reactivity of compounds 1 with palladium(II) acetate has allowed the isolation of complexes (mu-AcO)2[Pd{kappa2-C,N-C6H 3-4-R-1-[(3,5-Me2-C3N2)-CH 2-(eta5-C5H4)Fe(eta5-C 5H5)]}]2 (2) [R = OMe (2a) or H (2b)] that contain a bidentate [C(sp2, phenyl), N]- ligand and a central “Pd(mu-AcO)2Pd” unit.Furthermore, treatment of 2 with LiCl produced complexes (mu-Cl)2[Pd{kappa2-C,N-C6H 3-4-R-1-[(3,5-Me2-C3N2)-CH 2-(eta5-C5H4)Fe(eta5- C5H5)]}]2 (3) [R = OMe (3a) or H (3b)] that arise from the replacement of the acetato ligands by the Cl-.Compounds 2 and 3 also react with PPh3 giving the monomeric complexes [Pd{kappa2-C,N-C6H3-4-R-1-[(3,5-Me 2-C3N2)-CH2-(eta5- C5H4)Fe(eta5-C5H 5)]}X(PPh3)] {X- = AcO- and R = OMe (5a) or H (5b) or X- = Cl- and R = OMe (6a) or H (6b)}, where the phosphine is in a cis-arrangement to the metallated carbon atom. Treatment of 3 with thallium(I) acetylacetonate produced [Pd{kappa2-C,N-C6H3-4-R-1-[(3,5-Me 2-C3N2)-CH2-(eta5- C5H4)Fe(eta5-C5H 5)]}(acac)] (7) [R = OMe (7a) or H (7b)]. Electrochemical studies of the free ligands and the cyclopalladated complexes are also reported. The dimeric complexes 3 also react with MeO2C-C{triple bond, long}C-CO2Me (in a 1:4 molar ratio) giving [Pd{(MeO2C-C{double bond, long}C-CO2Me)2C6H3-4-R-1-[(3 ,5-Me2-C3N2)-CH2-(eta 5-C5H4)Fe(eta5-C5H 5)]}Cl] (8) [R = OMe (8a) or H (8b)], which arise from the bis(insertion) of the alkyne into the sigma{Pd-C(sp2, phenyl)} bond of 3.

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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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Exclusively planar chirality is exhibited by the ferrocenes obtained in a highly enantioselective synthesis in which a chiral aminoamide acts as a temporary protecting/directing group. This method was used to obtain an enantiomerically pure tetrasubstituted ferrocene, which was transformed into the first C2-symmetric disubstituted ferrocenophane [Eq. (1)].

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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 label-free method that can doubly image both the physical patterns and the electrochemical information of latent fingerprints (LFPs) on nitrocellulose (NC) membrane has been achieved here by water and scanning electrochemical microscopy (SECM). In this approach, the NC membrane with LFP (LFP/NC) sample was first placed in water, where the different absorption of water onto relatively hydrophobic ridge residues of LFP versus NC membrane background resulted in a high-resolution physical ridge pattern of the fingerprint to naked eyes within just 1?3 s and could further be photographed by a digital camera. Thereafter, the LFP/NC sample was electrochemically imaged by recording the current variations of SECM tip scanning over the label-free fingerprint in the surface-interrogation (SI) mode. The methyl viologen (MV2+) was chosen as the redox mediator to react selectively with the electroactive species in the fingerprint ridge residues rather than furrow regions, which could cause the sharp contrast of the SECM tip current for imaging. Both the collected physical and electrochemical images of LFPs can provide high resolution up to level 2 and level 3 features required for personal identification. In addition, for the first time commercial NC membrane instead of adhesive forensic tape was discovered here for lifting the LFPs from various surfaces, which can then be imaged by this electrochemical approach. Taken together, this method demonstrates a powerful strategy for directly imaging the electrochemical information in LFPs without damaging the fingerprint physical ridge pattern on various substrates, so it has great potentiality in individual identity related applications.

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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