A room-temperature-stable electride and its reactivity: Reductive benzene/pyridine couplings and solvent-free Birch reductions

Davison, Nathan; Quirk, James A.; Tuna, Floriana; Collison, David; McMullin, Claire L.; Michaels, Hannes; Morritt, George H.; Waddell, Paul G.; Gould, Jamie A.; Freitag, Marina; Dawson, James A.; Lu, Erli

doi:10.1016/j.chempr.2022.11.006

Cited by 31 publications

(45 citation statements)

References 77 publications

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“…Since 2022, a few groups, including us, started introducing mechanochemical ball milling 155–157 into alkali metal chemistry. The early effort has already led to exciting discoveries, such as new room-temperature stable alkali metal electride 158 and solvent-free Birch reductions. 158,159…”

Section: Discussionmentioning

confidence: 99%

“…The early effort has already led to exciting discoveries, such as new room-temperature stable alkali metal electride 158 and solvent-free Birch reductions. 158,159…”

Section: Discussionmentioning

confidence: 99%

“…Since 2022, a few groups, including us, started introducing mechanochemical ball milling [155][156][157] into alkali metal chemistry. The early effort has already led to exciting discoveries, such as new room-temperature stable alkali metal electride 158 and solvent-free Birch reductions. 158,159 The more pieces of the 'jigsaw' we have, the better our understanding and to be comprehensive both the solid-and solution-state structure (aggregation state and dynamic behav-…”

Section: Discussionmentioning

confidence: 99%

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The quest for organo-alkali metal monomers: unscrambling the structure–reactivity relationship

Davison

2023

Dalton Trans.

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Section: Discussionmentioning

confidence: 99%

“…The early effort has already led to exciting discoveries, such as new room-temperature stable alkali metal electride 158 and solvent-free Birch reductions. 158,159…”

Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

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The quest for organo-alkali metal monomers: unscrambling the structure–reactivity relationship

Davison

2023

Dalton Trans.

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“…In particular, reactions involving reduction steps remain poorly understood, in particular those purely based on metallic species [ 104 ]. However, recent studies in the mechanochemical preparation of highly reducing species, such as electrides, might open the path to and increase understanding of these processes [ 105 ].…”

Section: Redox Reactionsmentioning

confidence: 99%

Shaking Things from the Ground-Up: A Systematic Overview of the Mechanochemistry of Hard and High-Melting Inorganic Materials

Auvray

Friščić

2023

Molecules

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We provide a systematic overview of the mechanochemical reactions of inorganic solids, notably simple binary compounds, such as oxides, nitrides, carbides, sulphides, phosphides, hydrides, borides, borane derivatives, and related systems. Whereas the solid state has been traditionally considered to be of little synthetic value by the broader community of synthetic chemists, the solid-state community, and in particular researchers focusing on the reactions of inorganic materials, have thrived in building a rich and dynamic research field based on mechanically-driven transformations of inorganic substances typically seen as inert and high-melting. This review provides an insight into the chemical richness of such mechanochemical reactions and, at the same time, offers their tentative categorisation based on transformation type, resulting in seven distinct groupings: (i) the formation of adducts, (ii) the reactions of dehydration; (iii) oxidation–reduction (redox) reactions; (iv) metathesis (or exchange) reactions; (v) doping and structural rearrangements, including reactions involving the reaction vessel (the milling jar); (vi) acid–base reactions, and (vii) other, mixed type reactions. At the same time, we offer a parallel description of inorganic mechanochemical reactions depending on the reaction conditions, as those that: (i) take place under mild conditions (e.g., manual grinding using a mortar and a pestle); (ii) proceed gradually under mechanical milling; (iii) are self-sustained and initiated by mechanical milling, i.e., mechanically induced self-propagating reactions (MSRs); and (iv) proceed only via harsh grinding and are a result of chemical reactivity under strongly non-equilibrium conditions. By elaborating on typical examples and general principles in the mechanochemistry of hard and high-melting substances, this review provides a suitable complement to the existing literature, focusing on the properties and mechanochemical reactions of inorganic solids, such as nanomaterials and catalysts.

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“…Herein, we report the proof-of-concept of an unexplored approach to demonstrate the selective reduction of K + or Li + , employing the nonbinding "free" electrons in the Li-K heterobimetallic electride K + [LiN(SiMe 3 ) 2 ]e − (1) 17 Before moving onto our findings, we would like to introduce a class of highly unusual negative oxidation state Group-1 metal complexes, namely, alkalide, which feature M − centers (M: Na, K, Rb, Cs). 18−30 These species are prepared by treating zero-valent Group-1 metals with chelating reagents/ solvents (L), following a disproportionation route, i.e., 2M(0)…”

mentioning

confidence: 99%

Reduction of K⁺ or Li⁺ in the Heterobimetallic Electride K⁺[LiN(SiMe₃)₂]e^–

Davison

Waddell

2023

J. Am. Chem. Soc.

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Given their very negative redox potential (e.g., Li + → Li(0), −3.04 V; K + → K(0), −2.93 V), chemical reduction of Group-1 metal cations is one of the biggest challenges in inorganic chemistry: they are widely accepted as irreducible in the synthetic chemistry regime. Their reduction usually requires harsh electrochemical conditions. Herein we suggest a new strategy: via a heterobimetallic electride intermediate and using the nonbinding "free" electron as reductant. Based on our previously reported K + [LiN(SiMe 3 ) 2 ]e − heterobimetallic electride, we demonstrate the reducibility of both K + and Li + cations. Moreover, we find that external Lewis base ligands, namely tris[2-(dimethylamino)ethyl]amine (Me 6 Tren) or 2,2,2-cryptand, can exert a level of reducing selectivity by preferably binding to Li + (Me 6 Tren) or K + (2,2,2-cryptand), hence pushing the electron to the other cation.

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A room-temperature-stable electride and its reactivity: Reductive benzene/pyridine couplings and solvent-free Birch reductions

Cited by 31 publications

References 77 publications

The quest for organo-alkali metal monomers: unscrambling the structure–reactivity relationship

The quest for organo-alkali metal monomers: unscrambling the structure–reactivity relationship

Shaking Things from the Ground-Up: A Systematic Overview of the Mechanochemistry of Hard and High-Melting Inorganic Materials

Reduction of K⁺ or Li⁺ in the Heterobimetallic Electride K⁺[LiN(SiMe₃)₂]e^–

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A room-temperature-stable electride and its reactivity: Reductive benzene/pyridine couplings and solvent-free Birch reductions

Cited by 31 publications

References 77 publications

The quest for organo-alkali metal monomers: unscrambling the structure–reactivity relationship

The quest for organo-alkali metal monomers: unscrambling the structure–reactivity relationship

Shaking Things from the Ground-Up: A Systematic Overview of the Mechanochemistry of Hard and High-Melting Inorganic Materials

Reduction of K+ or Li+ in the Heterobimetallic Electride K+[LiN(SiMe3)2]e–

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Product

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Reduction of K⁺ or Li⁺ in the Heterobimetallic Electride K⁺[LiN(SiMe₃)₂]e^–