Three Reagents In One: Ammonium Permanganate In The Oxidation Of Benzyl Alcohol

Kótai, László; Kazinczy, Béla; Keszler, Ágnes; Holly, S.; Gács, István; Banerji, Kalyan K.

doi:10.1515/znb-2001-0816

Cited by 15 publications

(5 citation statements)

References 21 publications

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“…It is known that benzonitrile can be formed in the oxidation of benzyl alcohol with ammonium permanganate, 48 where the amount of ammonia needed for the ammoxidation reaction is rather limited to yield nitrile due to the stoichiometry (1:1) of NH 4 MnO 4 . In our case, the urea content of compound 1 is the source of ammonia.…”

Section: Resultsmentioning

confidence: 99%

Thermally Induced Solid-Phase Quasi-Intramolecular Redox Reactions of [Hexakis(urea-O)iron(III)] Permanganate: An Easy Reaction Route to Prepare Potential (Fe,Mn)O_x Catalysts for CO₂ Hydrogenation

et al. 2022

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Research on new reaction routes and precursors to prepare catalysts for CO 2 hydrogenation has enormous importance. Here, we report on the preparation of the permanganate salt of the urea-coordinated iron(III), [hexakis(urea- O )iron(III)]permanganate ([Fe(urea-O) 6 ](MnO 4 ) 3 ) via an affordable synthesis route and preliminarily demonstrate the catalytic activity of its (Fe,Mn)O x thermal decomposition products in CO 2 hydrogenation. [Fe(urea-O) 6 ](MnO 4 ) 3 contains O-coordinated urea ligands in octahedral propeller-like arrangement around the Fe 3+ cation. There are extended hydrogen bond interactions between the permanganate ions and the hydrogen atoms of the urea ligands. These hydrogen bonds serve as reaction centers and have unique roles in the solid-phase quasi-intramolecular redox reaction of the urea ligand and the permanganate anion below the temperature of ligand loss of the complex cation. The decomposition mechanism of the urea ligand (ammonia elimination with the formation of isocyanuric acid and biuret) has been clarified. In an inert atmosphere, the final thermal decomposition product was manganese-containing wuestite, (Fe,Mn)O, at 800 °C, whereas in ambient air, two types of bixbyite (Fe,Mn) 2 O 3 as well as jacobsite (Fe,Mn) T-4 (Fe,Mn) OC-6 2 O 4 ), with overall Fe to Mn stoichiometry of 1:3, were formed. These final products were obtained regardless of the different atmospheres applied during thermal treatments up to 350 °C. Disordered bixbyite formed first with inhomogeneous Fe and Mn distribution and double-size supercell and then transformed gradually into common bixbyite with regular structure (and with 1:3 Fe to Mn ratio) upon increasing the temperature and heating time. The (Fe,Mn)O x intermediates formed under various conditions showed catalytic effect in the CO 2 hydrogenation reaction with <57.6% CO 2 conversions and <39.3% hydrocarbon yields. As a mild solid-phase oxidant, hexakis(urea- O )iron(III) permanganate, was found to be selective in the transformation of (un)substituted benzylic alcohols into benzaldehydes and benzonitriles.

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Section: Resultsmentioning

confidence: 99%

Thermally Induced Solid-Phase Quasi-Intramolecular Redox Reactions of [Hexakis(urea-O)iron(III)] Permanganate: An Easy Reaction Route to Prepare Potential (Fe,Mn)O_x Catalysts for CO₂ Hydrogenation

et al. 2022

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“…The addition of coordinating solvents to substitute ammonia in the coordination sphere of the complex cation (DMF or CH 3 CN) suppressed the nitrile formation due to the stable solvated ammine complex formation [65]. It shows that the stability of the NH 3 source is a key factor in the ammoxidation reactions of benzyl alcohol into benzonitrile because the ammonium permanganate [99] or [hexakis(urea)iron(III)] permanganate (urea acts as ammonia precursor) [11] results in much more benzonitrile formation than the [tetraamminecopper(II)] permanganate [65].…”

Section: Tetraammine Complexesmentioning

confidence: 99%

Review on the Chemistry of [M(NH3)n](XO4)m (M = Transition Metal, X = Mn, Tc or Re, n = 1–6, m = 1–3) Ammine Complexes

Mehrotra

2023

Inorganics

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The preparation of ammine complexes of transition metals having oxidizing anions such as permanganate and perrhenate ions is a great challenge due to possible reactions between ammonia and oxidizing anions during the synthesis of these materials. However, it has an important role in both the development of new oxidants in organic chemistry and especially in the preparation of mixed-metal oxide catalyst precursors and metal alloys for their controlled temperature decomposition reactions. Therefore, in this paper, synthetic procedures to prepare ammonia complexes of transition metal permanganate, pertechnetate, and perrhenate (the VIIB group tetraoxometallates) salts have been comprehensively reviewed. The available data about these compounds’ structures and spectroscopic properties, including the presence of hydrogen bonds that act as redox reaction centers during thermal decomposition, are given and evaluated in detail. The nature of the thermal decomposition products has also been summarized. The available information about the role of the ammine complexes of transition metal permanganate salts in organic oxidation reactions, such as the oxidation of benzyl alcohols and regeneration of oxo-compounds from oximes and phenylhydrazones, including the kinetics of these processes, has also been collected. Their physical and chemical properties, including the thermal decomposition characteristics of known diammine (Ag(I), Cd, Zn, Cu(II), Ni(II)), triammine (Ag(I)), and simple or mixed ligand tetraammine (Cu(II), Zn, Cd, Ni(II), Co(II), Pt(II), Pd(II), Co(III)), Ru(III), pentaammine (Co(III), Cr(III), Rh(III) and Ir(III)), and hexaammine (Ni(II), Co(III), Cr(III)) complexes of transition metals with tetraoxometallate(VII) anions (M = Mn, Tc and Re), have been summarized. The preparation and properties of some special mixed ligand/anion/cation-containing complexes, such as [Ru(NH3)4(NO)(H2O)](ReO4)2, [Co(NH3)5(H2O)](ReO4)2, [Co(NH3)5X](MnO4)2 (X = Cl, Br), [Co(NH3)6]Cl2(MnO4), [Co(NH3)5ReO4]X2 (X = Cl, NO3, ClO4, ReO4), and K[Co(NH3)6]Cl2(MnO4)2, are also included.

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“…This reaction could be performed using two main types of oxidant. On the one hand, the utilization of metal oxides such as chromates [4,5] or permanganates [6,7] could lead to pollution by heavy metals in the desired product. Moreover, this process does not respect the principle of green chemistry since a really low atom efficiency is obtained, and a large quantity of waste is generated.…”

Section: Introductionmentioning

confidence: 99%

Naturally Nano: Magnetically Separable Nanocomposites from Natural Resources for Advanced Catalytic Applications

et al. 2022

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The present manuscript describes the use of silk cocoons as a structuring agent for the formation of an iron-based active phase for the controlled oxidation of benzyl alcohol. Different samples were prepared using different calcination temperatures. X-ray diffraction and transmission electron microscopy showed a higher proportion of alpha-Fe2O3 phase and a higher global crystallinity at superior calcination temperature. In terms of catalytic activity, the sample treated at 500 °C presented the highest conversion reaching 47%, with selectivity in benzaldehyde of 75.9%.

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Three Reagents In One: Ammonium Permanganate In The Oxidation Of Benzyl Alcohol

Cited by 15 publications

References 21 publications

Thermally Induced Solid-Phase Quasi-Intramolecular Redox Reactions of [Hexakis(urea-O)iron(III)] Permanganate: An Easy Reaction Route to Prepare Potential (Fe,Mn)O_x Catalysts for CO₂ Hydrogenation

Thermally Induced Solid-Phase Quasi-Intramolecular Redox Reactions of [Hexakis(urea-O)iron(III)] Permanganate: An Easy Reaction Route to Prepare Potential (Fe,Mn)O_x Catalysts for CO₂ Hydrogenation

Review on the Chemistry of [M(NH3)n](XO4)m (M = Transition Metal, X = Mn, Tc or Re, n = 1–6, m = 1–3) Ammine Complexes

Naturally Nano: Magnetically Separable Nanocomposites from Natural Resources for Advanced Catalytic Applications

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Three Reagents In One: Ammonium Permanganate In The Oxidation Of Benzyl Alcohol

Cited by 15 publications

References 21 publications

Thermally Induced Solid-Phase Quasi-Intramolecular Redox Reactions of [Hexakis(urea-O)iron(III)] Permanganate: An Easy Reaction Route to Prepare Potential (Fe,Mn)Ox Catalysts for CO2 Hydrogenation

Thermally Induced Solid-Phase Quasi-Intramolecular Redox Reactions of [Hexakis(urea-O)iron(III)] Permanganate: An Easy Reaction Route to Prepare Potential (Fe,Mn)Ox Catalysts for CO2 Hydrogenation

Review on the Chemistry of [M(NH3)n](XO4)m (M = Transition Metal, X = Mn, Tc or Re, n = 1–6, m = 1–3) Ammine Complexes

Naturally Nano: Magnetically Separable Nanocomposites from Natural Resources for Advanced Catalytic Applications

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Thermally Induced Solid-Phase Quasi-Intramolecular Redox Reactions of [Hexakis(urea-O)iron(III)] Permanganate: An Easy Reaction Route to Prepare Potential (Fe,Mn)O_x Catalysts for CO₂ Hydrogenation

Thermally Induced Solid-Phase Quasi-Intramolecular Redox Reactions of [Hexakis(urea-O)iron(III)] Permanganate: An Easy Reaction Route to Prepare Potential (Fe,Mn)O_x Catalysts for CO₂ Hydrogenation