Superelectrophilic chemistry in the gas phase

Roithová, Jana

doi:10.1351/pac-con-10-10-17

Cited by 22 publications

(13 citation statements)

References 18 publications

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“…Even stronger electrophilic character is needed for the spontaneous binding of noble gases (Ngs). Whereas some highly electrophilic cations can bind Xe, spontaneous Kr binding has almost exclusively been reported for dications . Such dications, referred to as superelectrophiles, play an important role in interstellar chemistry, and are elusive reaction intermediates, for example, in reactions involving alkane activation .…”

Section: Figurementioning

confidence: 99%

Superelectrophilic Behavior of an Anion Demonstrated by the Spontaneous Binding of Noble Gases to [B₁₂Cl₁₁]⁻

et al. 2017

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It is common and chemically intuitive to assign cations electrophilic and anions nucleophilic reactivity, respectively. Herein, we demonstrate a striking violation of this concept: The anion [B Cl ] spontaneously binds to the noble gases (Ngs) xenon and krypton at room temperature in a reaction that is typical of "superelectrophilic" dications. [B Cl Ng] adducts, with Ng binding energies of 80 to 100 kJ mol , contain B-Ng bonds with a substantial degree of covalent interaction. The electrophilic nature of the [B Cl ] anion is confirmed spectroscopically by the observation of a blue shift of the CO stretching mode in the IR spectrum of [B Cl CO] and theoretically by investigation of its electronic structure. The orientation of the electric field at the reactive site of [B Cl ] results in an energy barrier for the approach of polar molecules and facilitates the formation of Ng adducts that are not detected with reactive cations such as [C H ] . This introduces the new chemical concept of "dipole-discriminating electrophilic anions."

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Section: Figurementioning

confidence: 99%

Superelectrophilic Behavior of an Anion Demonstrated by the Spontaneous Binding of Noble Gases to [B₁₂Cl₁₁]⁻

et al. 2017

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“…Nevertheless, for hydrocarbon dications, it was shown that bond-forming reactions where twofold charge is preserved can represent the dominant reactivity channel [12,13]. The trick involves opening a low energy exit channel denoted by elimination of an H atom of a H 2 molecule [14][15][16].…”

Section: Introductionmentioning

confidence: 99%

Infrared spectroscopy of CHCl2+ molecular dications

Jašík

Roithová

2015

International Journal of Mass Spectrometry

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“…We do not experimentally observe proton transfer between benzaldehyde and [Yb(M) 3 (Tf )] 2+ because it is probably prevented by the Colomb barrier. [40]…”

Section: Gas Phase Experimentsmentioning

confidence: 99%

The Intermediates in Lewis Acid Catalysis with Lanthanide Triflates

Tripodi¹,

Correra

Angolini

et al. 2019

Eur J Org Chem

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Lanthanide triflates are effective Lewis acid catalysts in reactions involving carbonyl compounds due to their high oxophilicity and water stability. Despite the growing interest, the identity of the catalytic species formed in lanthanide catalysed reactions is still unknown. We have therefore used mass spectrometry and ion spectroscopy to intercept and characterize the intermediates in a reaction catalysed by ytterbium and dysprosium triflates. We were able to identify a number of lanthanide intermediates formed in a simple condensation reaction between a C‐acid and an aldehyde. Results show correlation between the reactivity of lanthanide complexes and their charge state and suggest that the triply charged complexes play a key role in lanthanide catalysed reactions. Spectroscopic data of the gaseous ions accompanied by theoretical calculations reveal that the difference between catalytic efficiencies of ytterbium and dysprosium ions can be explained by their different electrophilicity.

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Superelectrophilic chemistry in the gas phase

Cited by 22 publications

References 18 publications

Superelectrophilic Behavior of an Anion Demonstrated by the Spontaneous Binding of Noble Gases to [B₁₂Cl₁₁]⁻

Superelectrophilic Behavior of an Anion Demonstrated by the Spontaneous Binding of Noble Gases to [B₁₂Cl₁₁]⁻

Infrared spectroscopy of CHCl2+ molecular dications

The Intermediates in Lewis Acid Catalysis with Lanthanide Triflates

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Superelectrophilic chemistry in the gas phase

Cited by 22 publications

References 18 publications

Superelectrophilic Behavior of an Anion Demonstrated by the Spontaneous Binding of Noble Gases to [B12Cl11]−

Superelectrophilic Behavior of an Anion Demonstrated by the Spontaneous Binding of Noble Gases to [B12Cl11]−

Infrared spectroscopy of CHCl2+ molecular dications

The Intermediates in Lewis Acid Catalysis with Lanthanide Triflates

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Product

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Superelectrophilic Behavior of an Anion Demonstrated by the Spontaneous Binding of Noble Gases to [B₁₂Cl₁₁]⁻

Superelectrophilic Behavior of an Anion Demonstrated by the Spontaneous Binding of Noble Gases to [B₁₂Cl₁₁]⁻