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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

 

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A mononuclear non-heme manganese(V)-oxo complex, [MnV(O)(TAML)]- (1), was synthesized by activating dioxygen in the presence of olefins with weak allylic C-H bonds and characterized structurally and spectroscopically. In mechanistic studies, the formation rate of 1 was found to depend on the allylic C-H bond dissociation energies (BDEs) of olefins, and a kinetic isotope effect (KIE) value of 16 was obtained in the reactions of cyclohexene and cyclohexene-d10. These results suggest that a hydrogen atom abstraction from the allylic C-H bonds of olefins by a putative MnIV-superoxo species, which is formed by binding O2 by a high-spin (S = 2) [MnIII(TAML)]- complex, is the rate-determining step. A Mn(V)-oxo complex binding Sc3+ ion, [MnV(O)(TAML)]–(Sc3+) (2), was also synthesized in the reaction of 1 with Sc3+ ion and then characterized using various spectroscopic techniques. The binding site of the Sc3+ ion was proposed to be the TAML ligand, not the Mn-O moiety, probably due to the low basicity of the oxo group compared to the basicity of the amide carbonyl group in the TAML ligand. Reactivity studies of the Mn(V)-oxo intermediates, 1 and 2, in oxygen atom transfer and electron-transfer reactions revealed that the binding of Sc3+ ion at the TAML ligand of Mn(V)-oxo enhanced its oxidizing power with a positively shifted one-electron reduction potential (DeltaEred = 0.70 V). This study reports the first example of tuning the second coordination sphere of high-valent metal-oxo species by binding a redox-inactive metal ion at the supporting ligand site, thereby modulating their electron-transfer properties as well as their reactivities in oxidation reactions.

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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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In heterogeneous catalysis, catalysts provide a surface to which reactants bind in a process of adsorption. In homogeneous catalysis, catalysts are in the same phase as the reactants. Quality Control of 1,1′-Dibromoferrocene. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 1293-65-8, Name is 1,1′-Dibromoferrocene

A class of novel, easily accessible and air-stable 1-[bis(trifluoromethyl) phosphine]-1′-oxazolinylferrocene ligands has been synthesized from ferrocene. It became apparent that these ligands can be used in the regio- and enantioselective Pd-catalyzed allylic alkylation of monosubstituted allyl substrates in a highly efficient manner. Excellent regio- and enantioselectivity could be obtained for a wide range of substrates.

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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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In heterogeneous catalysis, catalysts provide a surface to which reactants bind in a process of adsorption. In homogeneous catalysis, catalysts are in the same phase as the reactants. Formula: C10Br2Fe. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 1293-65-8, Name is 1,1′-Dibromoferrocene

A convenient new method is developed for the preparation of 1?,1?-disubstituted biferrocenes which can be oxidized with iodine to a new series of mixed-valence compounds. The X-ray structures of 1?,1?-dimethoxymethyl, 1?,1?-diethoxyl, 1?,1?-dimethyl, 1?,1?-dihydroxymethyl, 1?,1?-dibenzoyloxymethyl, 1?,1?-dimethylthio, and 1?,1?-diethylthio neutral biferrocenes and the mixed-valence 1?,1?-diethoxyl, 1?,1?-dimethyl, 1?,1?-dibenzoyloxymethyl, and 1?,1?-diphenylthio biferrocenium triiodide salts have been determined at 298 K. The rates of intramolecular electron transfer in these mixed-valence cations were estimated by variable-temperature 57Fe Moessbauer experiment.

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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 metal coordination chemistry of a phosphine- and thiolate-substituted ferrocenediyl ligand were discussed. Bridged dimeric species, with the thiolate S adopting a binucleating role were found to be observed for Pd(II) and Rh(I) metal centers while a mononuclear, square planar Ni(II) complex was formed on reaction of the ligand with [Ni-(TMEDA)Me2]. It was found that the rhodium complexes with phosphorus-sulfur donor ligands showed excellent activities and stability as methanol carbonylation catalysts.

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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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1′,6′-Bis(stearoyloxy)biferrocene was synthesized and its Langmuir-Blodgett film was prepared, in which film the cyclopentadienyl rings of a ferrocene nucleus were orientated perpendicular to the film surface.Oxiadtion of the biferrocene derivative gave the mixed velence monocation complex which formed a stable monolayer on water.

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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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Compounds of the formula (I) in which R’1, R’2,R’3 and Het are each defined as specified in the description are obtainable in high yields by a stereoselective addition of R’3-substituted propionic esters onto R’1- and R’2-substituted unsaturated, bicyclic heterocyclylaldehydes of the formula R-CHO to give corresponding 3-(R)-3-hydroxy-2-R’3-propionic esters. Conversion of the OH group to a leaving group, a subsequent regioselective elimination to give 3-(R)-2-R’3-propenoic esters, followed by: 1) hydrolysis to the corresponding 3-(R)-2-R’3-propenoic acids, their enantioselective hydrogenation to corresponding chiral 3-(R)-2-R’3-propenoic acids and their reduction, or 2) hydrolysis to the corresponding 3-(R)-2-R’3-propenoic acids, their reduction to corresponding 3-(R)-2-R’3-allylalcohols and their enantioselective hydrogenation, or 3) reduction to corresponding 3-(R)-2-R’3-allylalcohols and their enantioselective hydrogenation, where R is formula (II) and the enantioselective hydrogenations are performed with metal complexes which have, as ligands, ferrocene-1,1′-diphosphines which have, in the 1-position, a ferrocene-substituted secondary phosphine group and, in the1′-position, a secondary phosphine group.

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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 that Mn(IV)-oxo porphyrin complexes, MnIV(O)(TMP) (1) and MnIV(O)(TDCPP) (2), are capable of activating the C-H bonds of hydrocarbons, including unactivated alkanes such as cyclohexane, via an oxygen non-rebound mechanism. Interestingly, 1 with an electron-rich porphyrin is more reactive than 2 with an electron-deficient porphyrin at a high temperature (e.g., 0 C). However, at a low temperature (e.g., -40 C), the reactivity of 1 and 2 is reversed, showing that 2 is more reactive than 1. To the best of our knowledge, the present study reports the first example of highly reactive Mn(IV)-oxo porphyrins and their temperature-dependent reactivity in C-H bond activation reactions.

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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 scalable access to functionalized ferrocenyl azides has been realized in flow. By halogen-lithium exchange of ferrocenyl halides and trapping with tosyl azide, a variety of functionalized ferrocenyl azides were obtained in high yields. To allow a scalable preparation of these potentially explosive compounds, a flow protocol was developed accelerating the reaction time to minutes and circumventing accumulation of potentially hazardous intermediates. The corresponding ferrocenyl amines were then prepared by a reliable reduction process.

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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 of 1-bromo-1?-aminoferrocene is reported using a simple synthetic methodology. This compound serves as a useful precursor to other heterosubstituted aminoferrocenes. For example, (1?-amino)ferrocenecarboxylic acid has been obtained and is conveniently isolated in its C-protected form by lithiation of 1-bromo-1?-aminoferrocene, quenching with solid carbon dioxide and esterification of the resulting carboxylate with methanolic HCl. The new ligand 1-diphenylphosphino-1?-aminoferrocene has also been obtained using a similar methodology.

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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