The “η-sweet-spot” (ηmax) in liquid-assisted mechanochemistry: polymorph control and the role of a liquid additive as either a catalyst or an inhibitor in resonant acoustic mixing (RAM) DOI
Lori Gonnet,

Tristan H. Borchers,

Cameron B. Lennox

et al.

Faraday Discussions, Journal Year: 2022, Volume and Issue: 241, P. 128 - 149

Published: Aug. 8, 2022

Resonant acoustic mixing (RAM) offers a simple, efficient route for mechanochemical synthesis in the absence of milling media or bulk solvents. Here, we show use RAM to conduct copper-catalysed coupling sulfonamides and carbodiimides. This was previously reported take place only by ball milling, while conventional solution environments it is not efficient, does at all. The results demonstrate as suitable methodology reactions accessed provide detailed, systematic overview how amount liquid additive, measured ratio volume weight reactants (η, μL mg-1), can affect course reaction polymorphic composition its product. Switching from allowed discovery new polymorph model sulfonylguanidine obtained catalytic di(cyclohexyl)carbodiimide (DCC) p-toluenesulfonamide, ability control temperature enabled situ behaviour this nascent We that conversion given time change monotonically but, instead, achieves maximum well-defined η-value. "η-sweet-spot" herein designated ηmax. explored sensitivity η on order 0.01 mg-1, which corresponds an additive below 5 mol% compared reactants, least one two orders magnitude lower than η-value typically considered design liquid-assisted reactions. Such suggests strategies optimise should systematically evaluate η-values increments even finer. At other ηmax drops off, demonstrating same act either catalyst inhibitor reaction, depending amount.

Language: Английский

Organic Reactions Enabled by Mechanical Force‐Induced Single Electron Transfer DOI
Ruoxuan Liu,

Xiaochun He,

Tianfen Liu

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(47)

Published: June 18, 2024

Mechanochemical reactions, achieved through milling, grinding, or other mechanical actions, have emerged as a solvent-free alternative to traditional solution-based chemistry. Mechanochemistry not only provides the opportunity eliminate bulk solvent use, reducing waste generation, but also unveils new reaction strategy which enables realization of reactions previously inaccessible in solution. While majority organic facilitated by force traditionally follow two-electron transfer pathways similar their counterparts, field mechanochemically induced single-electron (SET) has witnessed rapid development. This review outlines examples mechanochemical SET process, focusing on reagents that initiate SET, thereby positioning mechanochemistry burgeoning within realm

Language: Английский

Citations

6
Navigating Ball Mill Specifications for Theory‐to‐Practice Reproducibility in Mechanochemistry DOI Creative Commons
Orein F. Jafter, Sol Lee, Jongseong Park

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(48)

Published: Aug. 16, 2024

Abstract The rising prospects of mechanochemically assisted syntheses hold promise for both academia and industry, yet they face challenges in understanding and, therefore, anticipating respective reaction kinetics. Particularly, dependencies based on variations milling equipment remain little understood globally overlooked. This study aims to address this issue by identifying critical parameters through kinematic models, facilitating the reproducibility mechanochemical reactions across most prominent mills laboratory settings, namely planetary mixer mills. Through a series selected experiments replicating major classes organic, organometallic, transition metal‐catalyzed, inorganic from literature, we rationalize independence kinetics when accumulated energy criterion is met. As step forward facilitate practicability our findings, provide freely accessible online tool [†] that allows calculation different Our work advances current mechanochemistry lays foundation future rational exploration rapidly evolving field.

Language: Английский

Citations

6
Stainless steel-initiated chloro sulfoximidations of allenes under solvent-free conditions in a ball mill DOI

Deshen Kong,

Mostafa M. Amer, Carsten Bolm

et al.

Green Chemistry, Journal Year: 2022, Volume and Issue: 24(8), P. 3125 - 3129

Published: Jan. 1, 2022

Under solvent-free conditions in a mixer mill, sulfoximidoyl chlorides react with allenes by stainless steel-initiated radical addition reactions.

Language: Английский

Citations

27
From Inert to Catalytically Active Milling Media: Galvanostatic Coating for Direct Mechanocatalysis DOI Creative Commons
Maximilian Wohlgemuth,

Maike Mayer,

Marisol Fabienne Rappen

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(47)

Published: Sept. 13, 2022

The inert milling balls, commonly utilized in mechanochemical reactions, were coated with a layer of Pd and as catalyst the direct mechanocatalytic Suzuki reaction. With high yields (>80 %), balls can be recycled multiple times absence any solvents, ligands, catalyst-molecules -powders, while utilizing little 0.8 mg per ball. coating sequence, support material, thickness examined towards archiving retention, low abrasion conversion. approach was transferred to vessels revealing interplay between catalytically available surface area mechanical energy impact mechanocatalysis.

Language: Английский

Citations

24
The “η-sweet-spot” (ηmax) in liquid-assisted mechanochemistry: polymorph control and the role of a liquid additive as either a catalyst or an inhibitor in resonant acoustic mixing (RAM) DOI
Lori Gonnet,

Tristan H. Borchers,

Cameron B. Lennox

et al.

Faraday Discussions, Journal Year: 2022, Volume and Issue: 241, P. 128 - 149

Published: Aug. 8, 2022

Resonant acoustic mixing (RAM) offers a simple, efficient route for mechanochemical synthesis in the absence of milling media or bulk solvents. Here, we show use RAM to conduct copper-catalysed coupling sulfonamides and carbodiimides. This was previously reported take place only by ball milling, while conventional solution environments it is not efficient, does at all. The results demonstrate as suitable methodology reactions accessed provide detailed, systematic overview how amount liquid additive, measured ratio volume weight reactants (η, μL mg-1), can affect course reaction polymorphic composition its product. Switching from allowed discovery new polymorph model sulfonylguanidine obtained catalytic di(cyclohexyl)carbodiimide (DCC) p-toluenesulfonamide, ability control temperature enabled situ behaviour this nascent We that conversion given time change monotonically but, instead, achieves maximum well-defined η-value. "η-sweet-spot" herein designated ηmax. explored sensitivity η on order 0.01 mg-1, which corresponds an additive below 5 mol% compared reactants, least one two orders magnitude lower than η-value typically considered design liquid-assisted reactions. Such suggests strategies optimise should systematically evaluate η-values increments even finer. At other ηmax drops off, demonstrating same act either catalyst inhibitor reaction, depending amount.

Language: Английский

Citations

24