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The unusual nonbifunctional outer-sphere strategy was successfully utilized in developing an easily accessible N-heterocyclic carbene manganese (NHC-Mn) system for highly active alpha-alkylation of ketones with alcohols. This system was efficient for a wide range of ketones and alcohols under mild reaction conditions, and also for the green synthesis of quinoline derivatives. The direct outer-sphere mechanism and the high activity of the present system demonstrate the potential of nonbifunctional outer-sphere strategy in catalyst design for acceptorless dehydrogenative transformations.

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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 invention discloses a ferrocenyl pyrimidines ligand synthetic method and its application in the Heck reaction, in order to ferrocene, pyridine – 2 – formaldehyde and […] as raw materials, by acetylation, aldol condensation and condensation cyclization three-step reaction synthesis, synthesis method is simple in operation, mild condition, does not need to use expensive reagent, easy to large-scale preparation. The invention also relates to such ligands for the palladium-catalyzed coupling reaction of the Heck in application. The result shows that, ferrocenyl pyrimidines tridentate ligands 6 h with good thermal stability and high-efficiency catalytic activity. In the coupling reaction can be conducted under the conditions of the water as a solvent, the pervasive switching element substrate, without the need for tedious oxygen free operation. (by machine translation)

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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 report the electrocatalytic activity of ethylbenzene dehydrogenase (EBDH) from the beta-proteobacterium Aromatoleum aromaticum. EBDH is a complex 155 kDa heterotrimeric molybdenum/iron-sulfur/heme protein which catalyzes the enantioselective hydroxylation of nonactivated ethylbenzene to (S)-1-phenylethanol without molecular oxygen as cosubstrate. Furthermore, it oxidizes a wide range of other alkyl-substituted aromatic and heterocyclic compounds to their secondary alcohols. Hydroxymethylferrocenium (FM) is used as an artificial electron acceptor for EBDH in an electrochemically driven catalytic system. Electrocatalytic activity of EBDH is demonstrated with both its native substrate ethylbenzene and the related substrate p-ethylphenol. The catalytic system has been modeled by electrochemical simulation across a range of sweep rates and concentrations of each substrate, which provides new insights into the kinetics of the EBDH catalytic mechanism.

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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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Nanodiamond particles form agglomerates in the dry powder state and this poses limitation to the accessibility of their diamond-like core thus dramatically impacting their technological advancement. In this work, we report de-agglomeration of nanodiamond (ND) by using a facile technique namely, salt-assisted ultrasonic de-agglomeration (SAUD). Utilizing ultrasound energy and ionic salts (sodium chloride and sodium acetate), SAUD is expected to break apart thermally treated nanodiamond aggregates (~50-100 nm) and produce an aqueous slurry of de-aggregated stable colloidal nanodiamond dispersions by virtue of ionic interactions and electrostatic stabilization. Moreover, the SAUD technique neither has toxic chemicals nor is it difficult to remove impurities and therefore the isolated nanodiamonds produced are exceptionally suited for engineered nanocarbon for mechanical (composites, lubricants) and biomedical (bio-labeling, biosensing, bioimaging, theranostic) applications. We characterized the microscopic structure using complementary techniques including transmission electron microscopy combined with selected-area electron diffraction, optical and vibrational spectroscopy. We immobilized SAUD produced NDs on boron-doped diamond electrodes to investigate fundamental electrochemical properties. They included surface potential (or Fermi energy level), carrier density and mapping electrochemical (re)activity using advanced scanning electrochemical microscopy in the presence of a redox-active probe, with the aim of understanding the surface redox chemistry and the interfacial process of isolated nanodiamond particles as opposed to aggregated and untreated nanoparticles. The experimental findings are discussed in terms of stable colloids, quantum confinement and predominantly surface effects, defect sites (sp2-bonded C and unsaturated bonds), inner core (sp3-bonded C)/outer shell (sp2-bonded C) structure, and surface functionality. Moreover, the surface electronic states give rise to midgap states which serve as electron donors (or acceptors) depending upon the bonding (or antibonding). These are important as electroanalytical platforms for various electrocatalytic processes.

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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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Adsorption of analyte molecules is ubiquitous in nanofluidic channels due to their large surface-to-volume ratios. It is also difficult to quantify due to the nanometric scale of these channels. We propose a simple method to probe dynamic adsorption at electrodes that are embedded in nanofluidic channels or which enclose nanoscopic volumes. The amperometric method relies on measuring the amplitude of the fluctuations of the redox cycling current that arise when the channel is diffusively coupled to a bulk reservoir. We demonstrate the versatility of this new method by quantifying adsorption for several redox couples, investigating the dependence of adsorption on the electrode potential and studying the effect of functionalizing the electrodes with self-assembled monolayers of organothiol molecules bearing polar end groups. These self-assembled monolayer coatings are shown to significantly reduce the adsorption of the molecules on to the electrodes. The detection method is not limited to electrodes in nanochannels and can be easily extended to redox cycling systems that enclose very small volumes, in particular scanning electrochemical microscopy with nanoelectrodes. It thus opens the way for imaging spatial heterogeneity with respect to adsorption, as well as rational design of interfaces for redox cycling based sensors.

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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 intermolecular hydrogen bonding between 3-mercaptopropionic acid (MPA) and ferrocenylmethanol (FcCH2OH) on the tip electrode was studied by scanning electrochemical microscopy (SECM). The reversible assembly and disassembly of the intermolecular hydrogen bonding were designed with the aid of the dissociation equilibrium of the terminal carboxyl groups (-COOH) of the MPA self-assembled monolayer (SAM). Based on this design, the pH-modulated assembly and disassembly of intermolecular hydrogen bonding have been implemented. The use of well-defined SAM as model membrane provides a simple yet practicable approach to explore the molecular recognition at the cell membrane 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

 

Discovery of Ferrocenemethanol

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Well-defined side-chain ferrocene-containing polymers have been synthesized by post-modification of well-defined polyacrylonitrile (PAN). PAN prepared by Cu(0)-mediated single-electron transfer living radical polymerization was further modified using sodium azide and ammonium chloride (NH4Cl) to yield polymeric materials with vinyltetrazole units. Side-chain ferrocene-containing polymer was prepared by vinyltetrazole units and hydroxymethylferrocene after Mitsunobu reaction. FTIR, 1H NMR, UV?Vis spectroscopy and thermogravimetric analysis were used to identify the structure of the target product. After linked the ferrocene unit, the final polymer showed typical redox property with a more negative redox potential (E1/2).

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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 1273-86-5

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Optimized geometries and vOH stretching frequencies are reported for a set of monosubstituted ferrocenes, Fe(C5H5)(C 5H4R) [R = (CH2)nOH (n = 1-4), CH(Me)OH, CH(tBu)OH], at the BP86 level of density functional theory. In addition, NMR chemical shifts have been computed at the GIAO-B3LYP level. In all species studied, the most stable conformer is characterized by an OH…Fe moiety with Fe…H distances in the region between 2.61 and 2.95 A, followed by conformers with OH…pi interactions involving the C(ipso) atoms of the cyclopentadienyl ring. According to population and topological (Bader) analyses of the electron density, these conformers are stabilized by weak electrostatic interactions, rather than by true intramolecular hydrogen bonds. The VOH stretching frequencies are a very sensitive probe for the OH…Fe interaction, and the observed red-shift of this band relative to isomers with “free” OH bonds, which can exceed 100 cm-1, is well reproduced computationally. When other H-bond acceptors are present, the intramolecular OH…Fe interaction cannot compete with intermolecular H-bond formation, as has been explicitly shown in a Car-Parrinello molecular dynamics (CPMD) simulation of Fe(C5H5)-(C 5H4CH2OH) in water. Compared to these unconstrained ferrocene-containing alcohols, somewhat stronger OH…Fe interactions can be present in ansa derivatives, e.g., in a [2]ferrocenophane derivative with a CH2CH2OH group, for which a bond path between Fe and the alcoholic H atom is found.

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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 structure of protonated ferrocenes has been investigated using 1H NMR and 57Fe Moessbauer spectroscopy.The ketones were fully protonated in CF3CO2H and in 70percent H2SO4/H2O.In more concentrated sulphuric acid < > 90percent H2SO4/H2O) rapid heteroannular sulphonation occurred.No evidence was obtained of any iron protonation in these systems.For the para substituted aromatic derivatives C5H5FeC5H4COC6H4X the NMR data indicates steric inhibition to resonance. 1,1′-Diketones are doubly protonated in strongly acid media (98percent H2SO4, CF3SO3H).Moessbauer data on the solid ketones showed decrease in quadrupole splitting (QS), relative to ferrocene itself, of about 0.12 mm s-1 for each successive acyl function added.For solid solutions of the protonated ketones in CF3CO2H this decrease (DeltaQS) was much larger at about 0.28 mm s-1.The results are interpreted as involving electron withdrawal from ring-based orbitals (epsilon1), rather than the iron-based orbitals (epsilon2).In the aromatic series, DeltaQS was significantly smaller for electron withdrawing substituents.

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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

 

Top Picks: new discover of 1,1′-Dibromoferrocene

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2,4,6-Tris(1-diphenylphosphanyl-1?-ferrocenylene)-1,3,5-triazine (1) coordinates all three coinage metal(I) ions in a 1:1 tridentate coordination mode. The C3-symmetric coordination in both solid state and solution is stabilised by an uncommon cation?pi interaction between the triazine core and the metal cation. Intramolecular dynamic behaviour was observed by variable-temperature NMR spectroscopy. The borane adduct of 1, 1BH3, displays four accessible oxidation states, suggesting complexes of 1 to be intriguing candidates for redox-switchable catalysis. Complexes 1Cu, 1Ag, and 1Au display a more complicated electrochemical behaviour, and the electrochemical mechanism was studied by temperature-resolved UV/Vis spectroelectrochemistry and chemical oxidation.

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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