Gas-Phase Reactions of the Rhenium Oxide Anions, [ReOx]− (x = 2–4) with the Neutral Organic Substrates Methane, Ethene, Methanol and Acetic Acid

Canale, Valentino; Zavras, Athanasios; Khairallah, George N.; d’Alessandro, Nicola; O’Hair, Richard A. J.

doi:10.1255/ejms.1332

Cited by 10 publications

(9 citation statements)

References 69 publications

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“…We recently examined the gas-phase reactivity of the rhenium oxide anions, [ReO x ] – ( x = 2–4) toward the organic substrates: methane, ethylene, methanol, and acetic acid. Only [ReO 2 ] – and acetic acid reacted with [ReO 3 ] – being one of the products formed . The observation of this formal oxygen atom abstraction reaction occurring at near room temperature has prompted us to use a combination of gas-phase experiments and computational chemistry to examine whether CO 2 can be activated and cleaved in its reactions with [ReO 2 ] − .…”

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confidence: 99%

Two Spin-State Reactivity in the Activation and Cleavage of CO₂ by [ReO₂]⁻

Canale

Robinson

Zavras

et al. 2016

J. Phys. Chem. Lett.

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The rhenium dioxide anion [ReO2](-) reacts with carbon dioxide in a linear ion trap mass spectrometer to produce [ReO3](-) corresponding to activation and cleavage of a C-O bond. Isotope labeling experiments using [Re(18)O2](-) reveal that (18)O/(16)O scrambling does not occur prior to cleavage of the C-O bond. Density functional theory calculations were performed to examine the mechanism for this oxygen atom abstraction reaction. Because the spins of the ground states are different for the reactant and product ions ((3)[ReO2](-) versus (1)[ReO3](-)), both reaction surfaces were examined in detail and multiple [O2Re-CO2](-) intermediates and transition structures were located and minimum energy crossing points were calculated. The computational results show that the intermediate [O2Re(η(2)-C,O-CO2)](-) species most likely initiates C-O bond activation and cleavage. The stronger binding affinity of CO2 within this species and the greater instabilities of other [O2Re-CO2)](-) intermediates are significant enough that oxygen atom exchange is avoided.

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confidence: 99%

Two Spin-State Reactivity in the Activation and Cleavage of CO₂ by [ReO₂]⁻

Canale

Robinson

Zavras

et al. 2016

J. Phys. Chem. Lett.

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“…When trifluoroacetic acid is used, the binuclear molybdate anion, [Mo2O6(OH)] -, does react via step 1, but upon CID the resultant product, [Mo2O6(O2CCF3)] -, undergoes C-F bond activation instead to form [Mo2O6(F)] - (Khairallah et al, 2018). The rhenium oxide anions, [ReOx] -, react via quite different pathways with acetic acid: for those in higher oxidation states (x = 3 and 4) no reaction was observed, whereas [ReO2]promotes a complex series of C-X bond activation reactions (Canale et al, 2015).…”

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confidence: 99%

Organometallic Gas‐phase Ion Chemistry and Catalysis: Insights Into the Use of Metal Catalysts to Promote Selectivity in the Reactions of Carboxylic Acids and Their Derivatives

O’Hair

2020

Mass Spectrometry Reviews

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“…Nevertheless, owing to the extremely high stability of methane with strong C-H bonds, negligible electron affinity, large ionization energy, and low polarizability, the direct conversion of CH4 faces serious challenges. In gas-phase studies, the direct conversion of CH4 mediated by ionic species under isolated, controlled, and reproducible conditions is being actively studied [7][8][9][10][11][12][13] .…”

Section: Introductionmentioning

confidence: 99%

C―C Coupling of Methane Mediated by Atomic Gold Cations under Multiple-Collision Conditions

Ren¹,

中国科学院化学研究所²,

Liu³

et al. 2020

Acta Physico-Chimica Sinica

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The reactivity of atomic metal cations toward CH4 has been extensively investigated over the past decades. Closed-shell metal cations in electronically ground states are usually inert with CH4 under thermal collision conditions because of the extremely high stability of methane. With the elevation of collision energies, closed-shell atomic gold cations (Au + ) have been reported to react with CH4 under single-collision conditions to produce AuCH2 + , AuH + , and AuCH3+ species. Further investigations found that the ion-source-generated AuCH2 + cations can react with CH4 to synthesize C-C coupling products. These previous studies suggested that new products for the reaction of Au + with CH4 can be identified under multiple-collision conditions with sufficient collision energies. However, the reported ion-molecule reactions involving methane were usually performed under single-or multiple-collision conditions with thermal collision energies. In this study, a new reactor composed of a drift tube and ion funnel is constructed and coupled with a homemade reflectron time-of-flight mass spectrometer. Laser-ablation-generated Au + ions are injected into the reactor and drift 120 mm to react with methane seeded in the helium drift gas. The reaction products and unreacted Au + ions are focused through the ion funnel and accumulate through a linear ion trap and are then detected by a mass spectrometer. In the reactor, the pressure is approximately 100 Pa, and the electric field between the drift tube and ion funnel can regulate the collision energies between ions and molecules. The reaction of the closed-shell atomic Au + cation with CH4 is investigated, and the C-C coupling product AuC2H4 + is observed under multiple-collision conditions with elevated collision energies. Density functional theory calculations are performed to understand the mechanism of the coupling reaction (Au + + 2CH4 → AuC2H4 + + 2H2).Two pathways involving Au-CH2 and Au-CH3 species can separately mediate the C-C coupling process. The activation of the second C-H bond in each process requires additional energy to overcome the relatively high barrier (2.07 and 2.29 eV). Ion-trajectory simulations under multiple-collision conditions are then conducted to determine the collisional energy distribution in the reactor. These simulations confirmed that the electric fields between the drift tube and ion funnel could supply sufficient center-of-mass kinetic energies to facilitate the C-C coupling process to form AuC2H4 +

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Gas-Phase Reactions of the Rhenium Oxide Anions, [ReO_x]⁻ (x = 2–4) with the Neutral Organic Substrates Methane, Ethene, Methanol and Acetic Acid

Cited by 10 publications

References 69 publications

Two Spin-State Reactivity in the Activation and Cleavage of CO₂ by [ReO₂]⁻

Two Spin-State Reactivity in the Activation and Cleavage of CO₂ by [ReO₂]⁻

Organometallic Gas‐phase Ion Chemistry and Catalysis: Insights Into the Use of Metal Catalysts to Promote Selectivity in the Reactions of Carboxylic Acids and Their Derivatives

C―C Coupling of Methane Mediated by Atomic Gold Cations under Multiple-Collision Conditions

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Gas-Phase Reactions of the Rhenium Oxide Anions, [ReOx]− (x = 2–4) with the Neutral Organic Substrates Methane, Ethene, Methanol and Acetic Acid

Cited by 10 publications

References 69 publications

Two Spin-State Reactivity in the Activation and Cleavage of CO2 by [ReO2]−

Two Spin-State Reactivity in the Activation and Cleavage of CO2 by [ReO2]−

Organometallic Gas‐phase Ion Chemistry and Catalysis: Insights Into the Use of Metal Catalysts to Promote Selectivity in the Reactions of Carboxylic Acids and Their Derivatives

C―C Coupling of Methane Mediated by Atomic Gold Cations under Multiple-Collision Conditions

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Product

Resources

About

Gas-Phase Reactions of the Rhenium Oxide Anions, [ReO_x]⁻ (x = 2–4) with the Neutral Organic Substrates Methane, Ethene, Methanol and Acetic Acid

Two Spin-State Reactivity in the Activation and Cleavage of CO₂ by [ReO₂]⁻

Two Spin-State Reactivity in the Activation and Cleavage of CO₂ by [ReO₂]⁻