FeCl3 behavior in acetonitrile: structures of [FeCl2(CH3CN)4][FeCl4] and [AlCl(CH3CN)5][FeCl4]2.CH3CN

Gao, Yan; Guery, J.; Jacoboni, C.

doi:10.1107/s0108270192009892

Cited by 10 publications

(7 citation statements)

References 4 publications

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“…First-order dependency for FeCl 3 and zero-order dependency for 1 were observed (Figure e), which suggested that the nuclearity of the iron species was unchanged between the ground state and rate-determining transition state. Combined with the known structure A of FeCl 3 in MeCN, we propose the overall mechanism for oxidation shown in Figure f. Namely, zero-order in 1 implies rate-limiting internal reorganization in the dimeric ground-state structure A , which we propose involves a ligand dissociation to afford FeCl 4 – and FeCl 2 + (MeCN) 3 ( B ) .…”

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confidence: 99%

Structure and Reactivity of Aromatic Radical Cations Generated by FeCl₃

2019

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This paper describes the isolation and characterization of an aromatic radical cation generated by FeCl3. X-ray crystallographic analysis and kinetic studies reveal the mechanism of the generation of aromatic radical cation. In the solid state, a tight ion-pair of a radical cation with FeCl4 – is observed. Leveraging the efficient generation of the radical cation–FeCl4 – ion pair, we explore a radical cation-induced cycloaddition of trans-anethole initiated by catalytic amount of FeCl3. Both [4+2] cycloaddition and [2+2] cycloaddition with a broad substrate scope are also described. Moreover, a 100 g-scale reaction is demonstrated with the use of 1 mol % of FeCl3 as a simple and a highly active initiator.

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Structure and Reactivity of Aromatic Radical Cations Generated by FeCl₃

2019

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“…Our DFT calculations also pointed to the formation of relevant iron complexes. The ground state energy of the PBEh-3c optimized FeCl 3 , its dimeric species Fe 2 Cl 6 , and the [FeCl 4 ] − [FeCl 2 (CH 3 CN) 4 ] + and [FeCl 4 ] − [FeCl 2 (CH 3 CN) 2 ] + salts 27 (Figure S10e,f) were compared, including the solvent effects of MeCN, using the CPCM model. To compare the ground-state energy of the same number of atoms, also the energy of gas phase MeCN molecules was calculated and added (Figure 4a).…”

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confidence: 99%

Direct Synthesis of Acetone by Aerobic Propane Oxidation Promoted by Photoactive Iron(III) Chloride under Mild Conditions

et al. 2023

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C–H activation of hydrocarbons is extremely challenging, especially in short-chain hydrocarbons like propane. In industry, propane is first converted to propylene mostly by steam cracking, which is only oxidized to acetone in the cumene process, yielding acetone and phenol. In this work, we show that the simple FeCl3 salt in acetonitrile photocatalyzes the oxidation of propane to acetone at room temperature under aerobic conditions and visible-light irradiation. We achieved 100% conversion of propane with 67% selectivity in acetone after 4 h of irradiation and TON up to 600. Mechanistic studies, including electrospray ionization mass spectrometry, Mössbauer, and electroparamagnetic resonance spectroscopy, concluded that the reaction is driven by chlorine radicals generated by Fe–Cl bond photolysis. These results not only hold promise for the development of solar-based oxidation of hydrocarbons but more importantly also disclose deeper insights into the largely overlooked photochemistry of FeCl3.

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“…This is in agreement with a previous study on tetrachlorido ferrate compounds, reporting average bond lengths of 2.19 Å for the [FeCl 4 ] − anion and 2.29 Å for the [FeCl 4 ] 2− anion, with the Fe(II) variant showing a flattened tetrahedral structure. [25][26][27][28][29][30] The single crystal analysis resulted in a cation: anion ratio of 1:1. Consequently, as the N-butylpyridinium cation can only be charged +1, the oxidation state of iron has to be +3.…”

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confidence: 99%

Elucidating the Iron‐Based Ionic Liquid [C₄py][FeCl₄]: Structural Insights and Potential for Nonaqueous Redox Flow Batteries

Balischewski,

Bhattacharyya,

Bailey

et al. 2023

Adv Funct Materials

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In this study, a low‐melting organic‐inorganic crystalline ionic liquid compound, N‐butyl pyridinium tetrachlorido ferrate (III) is described. The material can easily be synthesized using a one‐pot approach in an ionic liquid medium. Single‐crystal X‐ray diffraction confirms that the basic inorganic block is [FeCl4]−, which is counterbalanced by an N‐butyl pyridinium cation. The compound exhibits a melting point of 37.6 °C by differential scanning calorimetry, which is among the lowest values for a pyridinium‐based metal‐containing ionic liquid. The material shows promising electrochemical behavior at room temperature in both aqueous and nonaqueous solvents, and at elevated temperatures in its pure liquid state. Given its appreciable solubility in both water and acetonitrile, the compound can act as a redox‐active species in a supporting electrolyte for redox flow battery applications. These classes of low‐melting ionic solids with long‐range order and interesting electrochemical applications are potential candidates for a range of green energy storage and harvesting systems.

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FeCl3 behavior in acetonitrile: structures of [FeCl2(CH3CN)4][FeCl4] and [AlCl(CH3CN)5][FeCl4]2.CH3CN

Cited by 10 publications

References 4 publications

Structure and Reactivity of Aromatic Radical Cations Generated by FeCl₃

Structure and Reactivity of Aromatic Radical Cations Generated by FeCl₃

Direct Synthesis of Acetone by Aerobic Propane Oxidation Promoted by Photoactive Iron(III) Chloride under Mild Conditions

Elucidating the Iron‐Based Ionic Liquid [C₄py][FeCl₄]: Structural Insights and Potential for Nonaqueous Redox Flow Batteries

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FeCl3 behavior in acetonitrile: structures of [FeCl2(CH3CN)4][FeCl4] and [AlCl(CH3CN)5][FeCl4]2.CH3CN

Cited by 10 publications

References 4 publications

Structure and Reactivity of Aromatic Radical Cations Generated by FeCl3

Structure and Reactivity of Aromatic Radical Cations Generated by FeCl3

Direct Synthesis of Acetone by Aerobic Propane Oxidation Promoted by Photoactive Iron(III) Chloride under Mild Conditions

Elucidating the Iron‐Based Ionic Liquid [C4py][FeCl4]: Structural Insights and Potential for Nonaqueous Redox Flow Batteries

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Structure and Reactivity of Aromatic Radical Cations Generated by FeCl₃

Structure and Reactivity of Aromatic Radical Cations Generated by FeCl₃

Elucidating the Iron‐Based Ionic Liquid [C₄py][FeCl₄]: Structural Insights and Potential for Nonaqueous Redox Flow Batteries