Mechanistic Insight into the Hydrogen Activation by Frustrated Lewis Pairs

Heshmat, Mojgan; Liu, Lei; Ensing, Bernd

doi:10.1007/978-3-030-58888-5_5

Cited by 6 publications

(3 citation statements)

References 102 publications

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“…Theoretical studies revealed that the reactivity of FLPs is strongly determined by the geometric parameters of Lewis acid (LA) and Lewis base (LB) complexes [17][18] .…”

Section: Introductionmentioning

confidence: 99%

Effects of Ionic Liquids on the Thermodynamics of Hydrogen Activation by Frustrated Lewis Pairs: A Density Functional Theory Study**

et al. 2021

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Nowadays, hydrogen activation by frustrated Lewis pairs (FLPs) and their applications are one of the emerging research topics in the field of catalysis. Previous studies have shown that the thermodynamics of this reaction is determined by electronic structures of FLPs and solvents. Herein, we investigated systems consisting of typical FLPs and ionic liquids (ILs), which are well known by their large number of types and excellent solvent effects. The density functional theory (DFT) calculations were performed to study the thermodynamics for H2 activation by both inter‐ and intra‐molecular FLPs, as well as the individual components. The results show that the computed overall Gibbs free energies in ILs are more negative than that computed in toluene. Through the thermodynamics partitioning, we find that ILs favor the H−H cleavage elemental step over the elemental steps of proton attachment, hydride attachment and zwitterionic stabilization. Moreover, the results show that these effects are strongly dependent on the type of FLPs, where intra‐molecular FLPs are more affected compared to the inter‐molecular FLPs.

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“…Theoretical studies revealed that the reactivity of FLPs is strongly determined by the geometric parameters of Lewis acid (LA) and Lewis base (LB) complexes [17][18] .…”

Section: Introductionmentioning

confidence: 99%

Effects of Ionic Liquids on the Thermodynamics of Hydrogen Activation by Frustrated Lewis Pairs: A Density Functional Theory Study**

et al. 2021

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“…The LA•••B distance in intramolecular FLPs is usually shorter than that in intermolecular ones, and typically it is in the same range as that of covalently bound LAÀ LB adducts. [27] The interaction of LA and LB in intramolecular FLPs typically plays an important role in reactions. In earlier reports of ethylene-bridged P/B FLP 9 (Scheme 3a), DFT calculations showed that the intramolecular P/B FLP formed a closed heterocyclic four-membered-ring structure through the weak interaction between P and B, which had two open isomers with different conformations.…”

Section: Lewis Acid/lewis Base Interactionmentioning

confidence: 99%

“…What’ s more, the most active intermolecular LA/LB combinations for H 2 cleavage are those that are not too far from each other and do not form a very large strong dative‐bond, with distances between reaction centers typically ranging from 1.6 Å to 6.0 Å. The LA⋅⋅⋅B distance in intramolecular FLPs is usually shorter than that in intermolecular ones, and typically it is in the same range as that of covalently bound LA−LB adducts [27] …”

Section: Key Aspects Of Flp Catalytic Hydrogenationmentioning

confidence: 99%

Design and Synthesis of Heterogeneous Frustrated Lewis Pairs for Hydrogenation: From Molecular Immobilization to Defects Engineering

Chen,

Wang,

2024

ChemCatChem

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The concept of “Frustrated Lewis pairs” (FLPs), which emerged from the discovery that H2 can be reversibly activated by combinations of sterically encumbered Lewis acids and bases. Since then, the field of FLP chemistry has expanded enormously. One of the most remarkable achievements is the development of FLP catalysts for hydrogenation, which are environmentally friendly and have potential industrial application prospects. In recent years, this unique catalysis concept has pushed the study of FLP chemistry to a new direction: heterogeneous FLP catalysts. This review outlines the recent research progress of new strategies to design and synthesize heterogeneous FLPs for hydrogenation reaction, and prospects the development of novel heterogeneous FLP catalysts.

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Dihydrogen Activation with a Neutral, Intermolecular Silicon(IV)‐Amine Frustrated Lewis Pair

Thorwart

Hartmann

Greb

2022

Chemistry A European J

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The heterolytic cleavage of dihydrogen constitutes the hallmark reaction of frustrated Lewis pairs (FLP). While being well‐established for planar Lewis acids, such as boranes or silylium ions, the observation of the primary H2 splitting products with non‐planar Lewis acid FLPs remained elusive. In the present work, we report bis(perfluoro‐N‐phenyl‐ortho‐amidophenolato)silane and its application in dihydrogen activation to a fully characterized hydridosilicate. The strict design of the Lewis acid, the limited selection of the Lewis base, and the distinct reaction conditions emphasize the narrow tolerance to achieve this fascinating process with a tetrahedral Lewis acid.

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Mechanistic Insight into the Hydrogen Activation by Frustrated Lewis Pairs

Cited by 6 publications

References 102 publications

Effects of Ionic Liquids on the Thermodynamics of Hydrogen Activation by Frustrated Lewis Pairs: A Density Functional Theory Study**

Effects of Ionic Liquids on the Thermodynamics of Hydrogen Activation by Frustrated Lewis Pairs: A Density Functional Theory Study**

Design and Synthesis of Heterogeneous Frustrated Lewis Pairs for Hydrogenation: From Molecular Immobilization to Defects Engineering

Dihydrogen Activation with a Neutral, Intermolecular Silicon(IV)‐Amine Frustrated Lewis Pair

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