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

 

Discovery of Ferrocenemethanol

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Chemical engineers ensure the efficiency and safety of chemical processes, adapt the chemical make-up of products to meet environmental or economic needs, and apply new technologies to improve existing processes. Quality Control of Ferrocenemethanol. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 1273-86-5, Name is Ferrocenemethanol

CAN-catalyzed reactions between alpha-ferrocenyl ethanol or ferrocenyl methanol and S-, N- and O-carborane nucleophiles are reported. This approach is an efficient and simple procedure for the preparation of carborane derivatives containing ferrocenyl units. Energy and geometry optimizations of some carboranylthio-, carboranylamino- and carboranyloxy-substituted ferrocenes have been calculated using the density functional theory. A series of new ferrocene-containing carborane 1,2,3-triazoles have been synthesized in good yields through a facile copper-mediated 1,3-dipolar cycloaddition reactions of alkynyl ferrocenes with [(o-carboran-1-yl)methyl]azide. Molecular structure of carborane-substituted ferrocenyl triazole was established by single crystal X-ray diffraction study. Representative examples of all ferrocenyl carboranes prepared were characterized by IR, 1H and 11B NMR 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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Multicomponent reactions are fundamentally different from two-component reactions, as multicomponent reactions can enable the efficient and step-economical construction of complex molecular scaffolds from simple precursors. Here, an unprecedented three-component direct C-H addition was achieved in the challenging meta-selective fashion. Fluoroalkyl halides and a wide range of alkenes, including vinylarenes, unactivated alkenes, and internal alkenes, were employed as the coupling partners of arenes in this strategy. The detailed mechanism presented is supported by kinetic isotope studies, radical clock experiments, and density functional theory calculations. Moreover, this strategy provided access to various fluoride-containing bioactive 1,1-diarylalkanes and other challenging synthetically potential products.

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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

 

Chemical Properties and Facts of 12180-80-2

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As a society publisher, everything we do is to support the scientific community – so you can trust us to always act in your best interests, Synthetic Route of 12180-80-2, and get your work the international recognition that it deserves. Introducing a new discovery about 12180-80-2, Name is 1,1′-Dibenzoylferrocene

The synthesis and mercuration of a series of Schiff bases 1?-benzoyl-1-[(arylimino)phenylmethyl]ferrocene (aryl: a variety of substituted phenyls) have been studied. In all cases the mercuration occurred at the 2-position of the ferrocene ring. Oxygen ? mercury coordinated products were not obtained. The X-ray crystal structure of [2-chloromercurio-1-[((phenylimino)phenylmethyl)-1?-benzoyl] ferrocene 5c has been determined; this crystallizes in the monoclinic, space group P21/c with a =10.168(3), b= 16.105(3), c = 15,463(4)A, beta = 103.61(2) and Z = 4. Refinement of atomic parameters gave an R factor of 0.038 (Romega = 0.055) for 2440 unique reflections having 1>3sigma(1). The structure confirms the formation of a five-membered metallocycle on the ferrocene moiety.

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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 1273-86-5

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Facile synthetic procedures to synthesize a series of difficult-To-obtain mercaptoalkylferrocenes, namely, Fc(CH2)nSH, where n = 1 (1), 2 (2), 3 (3), or 4 (4) and Fc = Fe(n5-C5H5)(n5-C5H4), are reported. Dimerization of 1-4 to the corresponding disulfides 19-22 was observed in air. Dimer 20 (Z = 2) crystallized in the triclinic space group Pi. Dimers 20-22 could be reduced back to the original Fc(CH2)nSH derivatives with LiAlH4 in refluxing tetrahydrofuran. Density functional theory (DFT) calculations showed that the highest occupied molecular orbital of 1-4 lies exclusively on the ferrocenyl group implying that the electrochemical oxidation observed at ca. -15 < Epa < 76 mV versus FcH/FcH+ involves exclusively an Fe(II) to Fe(III) process. Further DFT calculations showed this one-electron oxidation is followed by proton loss on the thiol group to generate a radical, Fc(CH2)nS, with spin density mainly located on the sulfur. Rapid exothermic dimerization leads to the observed dimers, Fc(CH2)n-S-S- (CH 2)nFc. Reduction of the ferrocenium groups on the dimer occurs at potentials that still showed the ferrocenyl group E = Epa,monomer - Epc,dimer ? 78 mV, indicating that the redox properties of the ferrocenyl group on the mercaptans are very similar to those of the dimer. 1H NMR measurements showed that, like ferrocenyl oxidation, the resonance position of the sulfhydryl proton, SH, and others, are dependent on -(CH2)n- chain length. Self-Assembled monolayers (SAMs) on gold were generated to investigate the electrochemical behavior of 1-4 in the absence of diffusion. Under these conditions, deltaE approached 0 mV for the longer chain derivatives at slow scan rates. The surface-bound ferrocenyl group of the metal-Thioether, Fc(CH)n -S-Au, is oxidized at approximately equal potentials as the equivalent CH2Cl2-dissolved ferrocenyl species 1-4. Surface coverage by the SAMs is dependent on alkyl chain length with the largest coverage obtained for 4, while the rate of heterogeneous electron transfer between SAM substrate and electrode was the fastest for the shortest chain derivative, Fc-CH2-S-Au. I am very proud of our efforts over the past few months, and hope to 1273-94-5 help many people in the next few years. .Synthetic Route of 1273-86-5

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 Vinylferrocene

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Mobile species transfer accompanying the redox switching of poly(vinylferrocene) (PVF) in aqueous perchlorate solutions of four cations was investigated using the electrochemical quartz crystal microbalance (EQCM). Cyclic voltammetry in 0.05 M solutions containing hydronium, sodium, rubidium or tetraethylammonium cation was employed. The mass transients could not be explained solely in terms of anion and solvent transport processes. EQCM transient data showed that the cation as well as perchlorate and water transport participated in the redox switching process in the four bathing solutions. Results and interpretation of the experimental approach are presented.

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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 kinetics of the oxygen reduction reaction (ORR) at carbon-supported transition-metal oxides in alkaline solutions is systematically investigated as a function of the nature of the B-site. The study is focused on LaBO3 (B=Cr, Co, Fe, Mn and Ni) nanoparticles synthesized by using an ionic-liquid route, offering fine control over phase purity and composition. Activity towards the ORR was compared with the commercial Pt/Etek catalyst. Detailed electrochemical analysis employing a rotating ring-disk electrode provides conclusive evidence that the carbon support plays an important contribution in the faradaic responses. Decoupling the contribution of the carbon support uncovers that the reactivity of LaMnO3 towards the four-electron ORR pathway is orders of magnitude higher than that for the other lanthanides. We rationalize these observations in terms of changes in the redox state at the B-site close to the formal oxygen reduction potential.

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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

 

Something interesting about Ferrocenemethanol

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The emergence of nanoscience and nanotechnology has opened up new horizons to researchers. In this regard, carbon nanomaterials are considered as the cornerstone of numerous investigations. Among various carbon nanostructures, ?Carbon nanoparticles (CNPs)? have attracted a great deal of attention during the past few years due to their unique properties such as high surface area, non-toxicity, biocompatibility as well as simple and low-cost synthetic procedures via environmentally friendly routes. Thanks to these properties along with their interesting optical behavior, CNPs have found diverse applications in the fields of bioimaging, nanomedicine, photo/electro-catalysis, and bio/chemical sensing. Moreover, their fascinating electrochemical properties including high effective surface area, excellent electrical conductivity, electrocatalytic activity as well as high porosity and adsorption capability, turn them to potential candidate for electrochemical purposes particularly sensing. The recent article, comprehensively reviews the usage of CNPs in design and construction of electrochemical sensors. It starts with a brief introduction of their properties and synthesis methods, then presents the electrode modification procedures, and finally come up with an overview of the proposed electrochemical sensing platforms based on CNPs. We hope that the recent review article will illuminate new lights in the minds of researchers active in this area and incorporates to promote the activities in this field of research.

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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 Ferrocenemethanol

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We have prepared a novel 3D porous biomaterial combining poly (dl-lactic acid) (PDLLA) and graphene and multi-walled carbon nanotubes oxides (MWCNTO-GO) composite. PDLLA as control and a high loading of PDLLA/MWCNTO-GO (50/50 w/w) bioscaffolds were prepared and functionalized. MWCNTs were exfoliated to form MWCNTO-GO by oxygen plasma etching. The later was also applied to enhance the scaffolds wettability, attaching oxygen-containing groups on their surfaces. This approach produced a porous architecture observed by scanning electron microscopy and semi-quantified by electrochemical analysis. The later also indicated a notable increase on the conductivity of PDLLA/MWCNTO-GO scaffold compared to MWCNTO-GO free PDLLA (about 5 orders of magnitudes at low frequencies). Thermogravimetric analysis showed that the MWCNTO-GO acted protecting the PDLLA matrix, enhancing its thermal stability. The PDLLA/MWCNTO-GO scaffolds had significant cellular adhesion, did not present cytotoxicity effect, besides reduced bactericidal proliferation and produced mineralized tissues in SBF media. The metallic MWCNTO-GO powder held together by PDLLA polymer opens a whole new branch of applications, including bioelectroanalyses, drug delivery systems and tissue engineering.

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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