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The t-butyl and bis(t-butyl) derivatives of hexathia[3.3]ferrocenophane were prepared from the corresponding trithia[3]ferrocenophanes. The former was a mixture of chair-chair and chair-boat isomers, and the latter existed only chair-boat isomer. The hexathia[3.3]ferrocenophanes were led to the tetrathiols with LiAlH4, which allowed to react with 1,1?-thiocarbonyldiimidazol to give the corresponding ferroceno[1?,2?;1?,2?]bis(1,3-dithiol-2-thione) derivatives. Mono t-butyl and unsubstituted analogs were prepared in a similar manner. The X-ray structural determination showed that these derivatives adopted the conformation in which the 1,3-dithiol-2-thione rings were heaped on top of each other. In the crystal of ferroceno[1?,2?;1?,2?]bis(1,3-dithiol-2-thione), the molecules packed so as to put the axis of molecule in order and to overlap one another above and below. The desulfurizative coupling of the ferroceno[1?,2?;1?,2?]bis(1,3-dithiol-2-thione) derivatives was unsuccessful.

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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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A series of dyads and triads using ferrocene (Fc) as the donor and 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) as the acceptor, linked either directly or through an N-phenylmethanimine or ethynylbenzene linker have been synthesized. While the former (directly linked) dyads were prepared through acid catalyzed condensation of pyrrole with ferrocenecarboxaldehye or 1,1?-ferrocenedicarboxaldehyde followed by oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), the latter two sets (imine and alkyne linked) of dyads were obtained through Schiff base condensation or Sonogashira coupling reactions, respectively. The compounds were fully characterized with spectroscopic data and single crystal X-ray analysis in one case. The peaks corresponding to the Fe(ii)/Fe(iii) redox couple at 0.33 to 0.38 V showed a varying degree of positive anodic shift, which reflected the strong electron withdrawing effect of the corresponding BODIPY unit. The first hyperpolarisability, beta, was measured in chloroform using the femtosecond hyper-Rayleigh scattering (HRS) method at 1300 nm. Interestingly, from the betaHRS values, the dominating role of the Fc donor and the intervening linker could be established, which correlated well with the experimental linear optical data as well as theoretical data calculated using density functional theory (DFT) and time-dependent DFT calculations. This work constitutes the first report where electron accepting power of BODIPY in combination with the Fc donor moiety, is exploited and we demonstrate that the values are comparable to that of push-pull derivatives where BODIPY was used as the conjugated linker.

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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

 

Never Underestimate The Influence Of 1,1′-Diacetylferrocene

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Ferrocenes bearing acyl substituents in the cyclopentadienyl rings [Fe(eta5-C5H4COR)(eta5-C 5H5)] and [Fe(eta5-C5H 4COR)2] (R = CH3, CF3 and Ph) were examined as new driers for solvent-borne alkyd binder. All studied ferrocenes were found to be active catalysts for cross-linking reaction of the alkyd. These iron(II) compounds give solid polymeric films with hardness and drying time comparable to the commercial cobalt(II) drier. Acetyl- and benzoyl-substituted ferrocenes show an excellent synergic effect with the cobalt drier giving hard polymeric films within short drying time. The kinetics of the alkyd autoxidation was followed by FTIR spectroscopy. Spin-trapping ESR technique has proven the important role of the ferrocenium cation upon decomposition of hydroperoxides by ferrocene-based driers. The peroxy and alkoxy radicals, appearing in drying process, were resolved by the new spin trap methyl-N-mesityl nitrone.

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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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Biogenic amines (BAs) have been reported in a variety of foods, such as fish, meat, cheese, and wines. The formation of BAs in food by the microbial decarboxylation of amino acids can result in human allergic reactions, characterized by difficulty in breathing, rash, vomiting, and hypertension. Control measures to prevent biogenic amine formation in foods and/or reduce their levels should be considered. Therefore, monitoring of BAs in food samples with the application of analytical techniques is of high importance. This review is based on literature data from 2010 until today and refers to food samples and alcoholic beverages. The rationale of this study is to provide data for the occurrence of BAs in food and beverages samples and a comparison of the analytical techniques and challenges in liquid and solid matrices. Importantly, BAs can be used as future markers for quality and freshness of the food products and alcoholic beverages.

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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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Features of the oxidation of hydroxymethylferrocene with molecular oxygen in organic solvent in the presence of weak and strong Broensted acids were studied. The resulting data were compared with published data on ferrocene and hydroxyferrocene oxidation, which made it possible to assess the trend in the oxidation mechanism in going from ferrocene pi complexes to their hydroxyferrocene and hydroxymethylferrocene analogs. A conclusion was drawn that each of the ferrocenes reacts with oxygen in quite a specific way.

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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

 

The Best Chemistry compound: Ferrocenemethanol

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The electrochemical behaviour of three ZrTi alloys (Zr5Ti, Zr25Ti and Zr45Ti) in Ringer’s solution has been investigated. Their resistance against localized corrosion has been determined from cyclic potentiodynamic polarization (CCP) and electrochemical impedance spectroscopy (EIS) measurements, whereas scanning electrochemical microscopy (SECM) was applied to investigate the local reactivity of the passive films developed on the materials, and scanning electron microscopy (SEM) was employed to characterize the surface morphology of the alloys subjected to anodic polarization. An increased reactivity could be detected with SECM when the metal samples were polarized at +0.50 V SHE, though the extent of this feature greatly depended on the nature of the metallic material. In addition, At 37 C, the Zr5Ti alloy was susceptible to localized corrosion. Though Zr25Ti alloy presented rather low pitting potential, the spontaneous corrosion potential of the material was sufficiently negative to require overpotentials around 600 mV for breakdown to occur. Finally, the Zr45Ti alloy exhibited a larger passive range in the polarization curve, and it was resistant to localized corrosion.

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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 introduce a three-way molecular motion which can be a suitable switching system in future molecule-based nanocircuits. A real-space investigation revealed that vinylferrocene adsorbs site-specifically on the Ge(100) surface and then shows a reversible tilting motion, similar to a seesaw. Unlike conventional molecular motions, it not only has three stable switching states at room temperature but also shows a motion-induced surface-structure modification, allowing surface-mediated signal transmission. Demonstrated STM-tip influence on the motion allows the feasibility of tip-induced manipulation.

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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

 

Never Underestimate The Influence Of Vinylferrocene

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The emergence of resistance against existing antileishmanial drugs necessitates the search for new classes of antileishmanial compounds. Herein a series of structurally diverse ferrocenylquinolines have been synthesized and evaluated for in vitro antileishmanial activity against Leishmania donovani using the MTT assay. Thirteen (M2-M14) substituted ferrocenylquinoline congeners possessing triazole rings were generated by palladium mediated Suzuki-Miyaura coupling reaction of 5-iodoferrocenylquinolinetriazole and substituted arylboronic acids. All the synthesized compounds were tested for its antileishmanial activity using both promastigote and amastigote stages of L. donovani. Among them, three compounds (M4, M7 and M9) exhibited promising anti-promastigote activity, with an IC50value of 28.7 muM, 22.1 muM and 28 muM, respectively, and no cytotoxicity toward host splenocytes. These three compounds are equally effective against the intracellular amastigote stage of L. donovani showing the IC50values of 16 muM (M4), 8 muM (M7) and 16 muM (M9), respectively, with consistent nitric oxide generation as required for parasite clearance. From the battery of tests conducted in this study, it appears that these compounds induce parasite death by promoting cell cycle arrest and triggering apoptosis.

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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 Shocking Revelation of 1,1′-Diacetylferrocene

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The complex [Rh(CO)2{HC(pz?)3}][PF6], 1 +[PF6]- {HC(pz?)3 = tris(3,5-dimethylpyrazolyl)methane}, prepared by reacting [{Rh(CO)2(mu-Cl)}2] with HC(pz?)3 in the presence of Tl[PF6], has a distorted square pyramidal structure with a kappa3-HC(pz?)3 ligand. Carbonyl substitution with Lewis bases gives [Rh(CO)L{HC(pz?)3}] [PF6] {L = PPh3, 2+[PF6]-; L = AsPh3, 3+[PF6]-; L = P(o-tolyl)3, 4+[PF6]-}, which have square planar kappa2 structures, confirmed by X-ray crystallography for 2+[PF6]-. The cations 2+ and 3+ have the third pyrazolyl ring orientated pseudo-parallel to the square planar metal whereas 4+ more likely has the third ring orientated exo to that plane. One-electron oxidation of 2+ and 3+ gives the Rh(II) dications [Rh(CO)(PPh3){HC(pz?)3}]2+, 22+, and [Rh(CO)(AsPh3){HC(pz?)3}]2+, 32+, characterised by ESR spectroscopy. Complex 1+[PF6]- reacts with PhC?CPh to give [Rh(CO)(eta2-PhC?CPh)-{HC(pz?)3}] [PF6], 5+[PF6]-, in which the two-electron donor alkyne occupies an equatorial position in a trigonal bipyramidal kappa3 structure. With MeC?CR (R = Me or Et), 1+[PF6]- gives the kappa2 square planar complexes [Rh{eta4-C4Me2R2C(O)}{HC(pz? )3}][PF6] (R = Me, 6+[PF6]-; R = Et, 7+[PF6]-) in which the cyclopentadienone ligands are coordinated via two Rh-monoalkene bonds; the structurally characterised form of 7+ has the two alkyne units linked head-to-head with the CEt termini bound to the ketonic CO group. With HC?CPh or HC?CH, 1+ gives the octahedral, kappa3 rhodium(III) metallacyclopentadienes [Rh(CO)(eta1:eta1?-CHCRCHCR) {HC(pz?)3}][PF6] (R = Ph, 8+[PF6]-; R = H, 9+[PF6]-) with the two alkynes linked head-to-tail in 8+. The reaction of 1+ with HC?CH also gives the cycloheptatrienone (tropone) derivative [Rh{eta4-C6H6C(O)}{HC(pz?)3} ][PF6], 10+[PF6]-, with a kappa3 ligand and the cycloheptatrienone ligand bound to the metal via two Rh-C sigma-bonds and one Rh-monoalkene interaction.

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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

 

What I Wish Everyone Knew About Vinylferrocene

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The aminocarbonylation of alkenes is a powerful method for accessing the beta-amino carbonyl motif that remains underdeveloped. Herein, the development of intermolecular aminocarbonylation reactivity of iminoisocyanates with alkenes is presented. This includes the discovery of a fluorenone-derived reagent, which was effective for many alkene classes and facilitated derivatization. Electron-rich substrates were most reactive, and this indicated that the LUMO of the iminoisocyanate is reacting with the HOMO of the alkene. Computational and experimental results support a concerted asynchronous [3 + 2] cycloaddition involving an iminoisocyanate, which was observed for the first time by FTIR under the reaction conditions. The products of this reaction are complex azomethine imines, which are precursors to valuable beta-amino carbonyl compounds such as beta-amino amides and esters, pyrazolones, and bicyclic pyrazolidinones. A kinetic resolution of the azomethine imines by enantioselective reduction (s = 13.43) allows access to enantioenriched products. Overall, this work provides a new tool to convert alkenes into beta-amino carbonyl compounds.

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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