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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. SDS of cas: 1273-94-5. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 1273-94-5, Name is 1,1′-Diacetylferrocene

The chiral Cd(II) complex {[Cd(L)(CH3COO)2(H2O)]H2O}n {L = 1,1′-[bis-3-(3-pyridyl)pyrazol-5-yl]ferrocene} has been synthesised. The Cd(II) ion is coordinated by two pyridyl nitrogen atoms, two chelating acetate anions and one water molecule, showing a distorted pentagonal-bipyramidal coordination environment. Each ligand L serves as a bisconnector, bridging two Cd atoms through its two pyridyl moieties, to afford an infinite 1D left-handed helical chain along the a-axis with a short pitch of 5.8761 (9) A. Moreover, all of the left-handed helical chains are joined by hydrogen bonds to form a left-handed homochiral crystal.

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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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The development of catalysts based on earth abundant metals in place of noble metals is becoming a central topic of catalysis. We herein report a cobalt/tetraphosphine complex-catalyzed homogeneous hydrogenation of polar unsaturated compounds using an air- and moisture-stable and scalable precatalyst. By activation with potassium hydroxide, this cobalt system shows both high efficiency (up to 24 000 TON and 12 000 h-1 TOF) and excellent chemoselectivities with various aldehydes, ketones, imines, and even N-heteroarenes. The preference for 1,2-reduction over 1,4-reduction makes this method an efficient way to prepare allylic alcohols and amines. Meanwhile, efficient hydrogenation of the challenging N-heteroarenes is also furnished with excellent functional group tolerance. Mechanistic studies and control experiments demonstrated that a CoIH complex functions as a strong hydride donor in the catalytic cycle. Each cobalt intermediate on the catalytic cycle was characterized, and a plausible outer-sphere mechanism was proposed. Noteworthy, external inorganic base plays multiple roles in this reaction and functions in almost every step of the catalytic cycle.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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A biosensor based on the immobilization of lactate oxidase (LOx) on a glassy carbon electrode modified with laponite/chitosan hydrogels for the quantification of l-lactate in alcoholic beverages and dairy products is presented. Ferrocene-methanol (FcMe) is used as artificial mediator. The purpose of this work is to determine the best hydrogel composition from the analytical point of view. The characterization of the hydrogels was carried out by CV, amperometry and EIS. According to permeabilities and charge transfer resistances for ferrocyanide (used as molecular probe) as well as the enzymatic behavior of the enzyme for l-lactate, the best laponite/chitosan mass ratio found was 25/50. The distinct features of the bioelectrode are its long stability, its ability to reject or minimize most interferents including ascorbic acid, and its excellent analytical response, which allowed the reduction of the enzyme content below 0.5 U, for a sensitivity of (0.326 ± 0.003) A cm -2 M-1, with a time response lower than 5 s and a detection limit of (3.8 ± 0.2) × 10-6 M. Our l-lactate biosensor was validated by comparison with a standard spectroscopic method.

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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 results of a systematic electrochemical study of the host-guest supramolecular adducts between ferrocene (Fc), ferrocenium cation (Fc+), and other mono- and disubstituted ferrocene derivatives with different beta-cyclodextrins (CD) in mixed organic-aqueous media. The influence on the formation constants (Kf) of the organic cosolvent, the different substituents on Fc, and the type of CDs are evaluated. NMR and conductometry responses of ferrocenium cation solutions in the presence of CD confirm the weak propensity of Fc+ to enter into the cyclodextrin cavity. The Kf value generally decreases as the steric bulk and the rigidity of Fc substituents increases, consistent with an inclusion model in which the Fc fits into the CD cavity in an axial mode while the substituent protrudes out. Interestingly, the addition of sulfated beta-CD shifts the redox Fc/Fc+ couple toward cathodic values, indicating that the oxidized, cationic form Fc+ is more strongly bound to the sulfated cyclodextrin than neutral Fc, probably by means of electrostatic interaction with the external -SO3- functionalities.

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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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The photolysis of 1,1?-diacylferrocenes Fc(COR)2 (Fc = Ferrocenyl, R = CH3,Ph) in the presence of 1,10-phenanthroline (phen) in deoxygenated acetonitrile under irradiation with visible light has been studied. In these photolysis systems the phen has two important roles to play: one is to stabilize the photo-liberated Fe2+ by coordination, and the other is to promote the photolysis through photo-ligand exchange. Under this condition the photoproducts were isolated in definite composition and characterized by single crystal X-ray diffraction, 1H NMR spectroscopy, IR spectroscopy, photolysis-cyclic voltammetry and elemental analysis. The mechanism of the reactions was demonstrated to be charge transfer from metal to acylcyclopentadienyl ring, leading to cleavage of the bond between them. The phen attacks the Fe2+ ion to give the stable tris (1,10-phenanthroline) iron(II) complex cation and the acylcyclopentadienyl ring detaches from the Fe2+ ion, giving the enolate anion in the outer sphere of the complex. Crystallographic data for photoproduct 1, [Fe(phen)3] (C5H4COCH3)2 ·CH3CN ·2H2O: triclinic, space group P-1 (No. 2), a=12.714(4), b=13.125(3), c= 14.946(5) A, alpha=106.45(1), beta=112.13(3), gamma=79.60(2). V=2208(1) A3, R = 0.041, RW = 0.052. Crystallographic data for photoproduct 2, [Fe(phen)3](C5H4COC6H 5)2 ·0.5C6H6 ·H2O: triclinic, space group P-1 (No. 2), a= 12.218 (4), b= 12.440 (3), c= 16.989 (2) A, alpha = 98.56(2), beta= 102.06(2), gamma= 100.98(3), V=2431(2) A3, R = 0.049, RW = 0.057.

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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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Moessbauer and NMR spectra are reported for ferrocenyl (Fc) carbenium ions, FcCH2+ (III+) and FcC+Me2 (II+) in frozen acidic media. 1H-NMR spectra showed no evidence of Fe-H bonded species.Moessbauer parameters for II+ were identical within experimental error to those obtained for the carbenium ion precursors and to ferrocene itself, whereas quadrupole splittings for III+ were significantly larger.The results for the latter species are interpreted in terms of stabilisation via orbital overlaps with the central iron atom.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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This work deals with the synthesis and evaluation of new compounds designed by combination of 1,4-naphthoquinone and ferrocene fragments in a 3-ferrocenylmethyl-2-hydroxy-1,4-naphthoquinone arrangement. A practical coupling reaction between 2-hydroxy-1,4-naphthoquinone and ferrocenemethanol derivatives has been developed. This procedure can be carried out “on-water”, at moderate temperatures and without auxiliaries or catalysts, with moderate to high yields. The synthesized derivatives have shown significant in vitro antiplasmodial activity against chloroquine-sensitive and resistant Plasmodium falciparum strains and it has been shown that this activity is not related to the inhibition of biomineralization of ferriprotoporphyrin IX. Binding energy calculations and docking of these compounds to cytochrome b in comparison with atovaquone have been performed.

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Conjugates of ferrocene and 4,5-dichloroisothiazole were synthesized, where the ferrocene and isothiazole moieties are linked through various structural fragments. The acylation of ferrocene with 4,5- dichloroisothiazole-3-carbonyl chloride gave (4,5-dichloroisothiazol-3-yl) ferrocenyl ketone; the acylation of aminomethylferrocene furnished the corresponding amide. The esterification of ferrocene-1,1?-dicarboxylic acid with 4,5-dichloroisothiazol-3-yl-methanol resulted in the formation of the corresponding ester. The condensation of 1,1?-diacetylferrocene with 4,5-dichloroisothiazole-3-carbaldehyde afforded ferrocenophane containing 4,5-dichloroisothiazole moieties.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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In the presence of tetrabutylammonium hydroxide as catalyst and at room temperature, ethyl ferrocenecarboxylate, ethyl ferrocenylacetate, ethyl 3-ferrocenylpropanoate, 1,1?-ferrocenyl-bis(ethyl propanoate), ethyl 3-ferrocenylpropenoate and 1,1?-ferrocenyl-bis(ethyl propenoate) undergoes facile transesterification reaction with aliphatic, benzyl and allyl alcohols to furnish the corresponding ferrocenyl esters in good to excellent yields. Ring closing metathesis of the ester Fc-1,1?-(CHCH-CO2CH 2CHCH2)2 yields the corresponding closed loop ferrocenyl ester.

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This paper addresses on the electrochemical behaviour of three TiMo alloys exposed to simulated physiological environments. Their stability and corrosion resistance was characterized in order to explore the potential application for the manufacturing of implant materials. Ringer’s solution together with an acidic modification of the Ringer’s solution (pH 3.1) at room temperature were considered. Both electrochemical methods (namely, potentiodynamic polarization curves and electrochemical impedance spectroscopy, EIS), and spatially resolved scanning electrochemical microscopy (SECM), were used. Additionally, surface characterization was made employing optical microscopy and scanning electron microscopy (SEM). The oxide films formed on the TiMo alloys in neutral and acidic Ringer’s solutions effectively protect the metal from dissolution in these environments, and no breakdown of the passive layer occurs in the potential range up to +1.00 V vs. SCE. SEM micrographs of retrieved samples do not show corrosion pits, cracks, or any other defects despite the rather high positive potential values reached during the potential excursion. EIS data reveal that two-layer oxide films are formed, consisting of a porous outer layer and a compact inner layer (approximately 5-6 nm thick), the latter accounting almost completely for the corrosion resistance of the materials. The corrosion resistance of the inner compact film towards metal dissolution is smaller in the acidic environment, whereas it increases with higher Mo contents in the alloy. The passive oxide films exhibit dielectric characteristics towards charge transfer when they are imaged by scanning electrochemical microscopy.

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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