2022
DOI: 10.1021/jacs.2c02471
|View full text |Cite
|
Sign up to set email alerts
|

Reactivity Differences of Rieke Zinc Arise Primarily from Salts in the Supernatant, Not in the Solids

Abstract: Contrary to prevailing thought, the salt content of supernatants is found to dictate reactivity differences of different preparation methods of Rieke zinc toward oxidative addition of organohalides. This conclusion is established through combined singleparticle microscopy and ensemble spectroscopy experiments, coupled with careful removal or keeping of the supernatants during Rieke zinc preparations. Fluorescence microscopy experiments with single-Riekezinc-particle resolution determined the microscale surface… Show more

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
2
1
1
1

Citation Types

0
9
0

Year Published

2022
2022
2024
2024

Publication Types

Select...
7
1

Relationship

3
5

Authors

Journals

citations
Cited by 14 publications
(16 citation statements)
references
References 41 publications
0
9
0
Order By: Relevance
“…Imaging agent 1 contains a boron dipyrromethene (BODIPY) fluorophore core and a carboxylic acid tail. The BODIPY core is a well-established hydrophobic fluorophore. This fluorophore class was chosen for present studies due to its hydrophobicity (which makes it a good model for representative organic additives), high quantum yield, small size relative to the micelles/vesicles, and established chemical inertness. ,, Specific amphiphilic imaging agent 1 was of particular interest due to the hydrophilic carboxylic acid group combined with its hydrophobic BODIPY core possessing an amphiphilicity that could inform on interactions between the organic substrate, surfactant, water, and reagents. 2-Iodoethylbenzene was chosen as a model organic substrate at 0.5 M, representative of the organohalide oxidative-addition partners and high substrate concentrations used preparatively in carbon–carbon cross-coupling reactions in water in the presence of zinc, palladium catalyst, and surfactants .…”
Section: Resultsmentioning
confidence: 99%
“…Imaging agent 1 contains a boron dipyrromethene (BODIPY) fluorophore core and a carboxylic acid tail. The BODIPY core is a well-established hydrophobic fluorophore. This fluorophore class was chosen for present studies due to its hydrophobicity (which makes it a good model for representative organic additives), high quantum yield, small size relative to the micelles/vesicles, and established chemical inertness. ,, Specific amphiphilic imaging agent 1 was of particular interest due to the hydrophilic carboxylic acid group combined with its hydrophobic BODIPY core possessing an amphiphilicity that could inform on interactions between the organic substrate, surfactant, water, and reagents. 2-Iodoethylbenzene was chosen as a model organic substrate at 0.5 M, representative of the organohalide oxidative-addition partners and high substrate concentrations used preparatively in carbon–carbon cross-coupling reactions in water in the presence of zinc, palladium catalyst, and surfactants .…”
Section: Resultsmentioning
confidence: 99%
“…The faint fluorescence on the surface of the zinc from 6 derives from the minor physisorption of this compound to the zinc surface, 8. [35][36][37]39,40] Second, TMSCl was added, the samples were swirled to mix, and then immediately imaged. Trimethylsilyl chloride produced an immediate solubilization of the surface organometallic intermediate 7, as seen by removal of the fluorescent material from zinc surface (image representative of spatial survey of sample shown).…”
Section: Methodsmentioning
confidence: 99%
“…20,21 In the 1970s, Rieke pioneered an elegant solution to these practical problems of efficiency and generality for several alkaline earth and transition metals such as magnesium, zinc, and copper by developing a method that allowed access to highly reactive metal powders via the reduction of metal salts with alkali metals (Figure 1C). 22,23 Beyond the obvious synthetic utility of preparing reactive metals freshly, Rieke's method was practical and straightforward, making it an instant success among the chemistry community. Unfortunately, Limetal bears the lowest reduction potential among the elements and therefore cannot be prepared using Rieke's method.…”
Section: Preparation Of Reactive Metal Powdersmentioning
confidence: 99%
“…In the realm of organometallic chemistry, the transfer of electrons from a metal to an organic substrate is the quintessential process to form carbon–metal bonds (Figure B) . However, because the reactions are heterogeneous, variabilities in the quality and area of the metal surface often render these processes unpredictable and facetious in nature, especially on routine laboratory scales. , Historically, reaction development in this field has relied on activating the metal by mechanically reducing the size of the metal particle and by adding chemical activators such as iodine to clean the metal surface. , In the 1970s, Rieke pioneered an elegant solution to these practical problems of efficiency and generality for several alkaline earth and transition metals such as magnesium, zinc, and copper by developing a method that allowed access to highly reactive metal powders via the reduction of metal salts with alkali metals (Figure C). , Beyond the obvious synthetic utility of preparing reactive metals freshly, Rieke’s method was practical and straightforward, making it an instant success among the chemistry community. Unfortunately, Li-metal bears the lowest reduction potential among the elements and therefore cannot be prepared using Rieke’s method. As a departure from the current synthetic logic of mechanically pulverizing known Li-metal sources into reactive powders, we sought a new chemical approach which would allow for distinctive Li-metal sources to be practically prepared.…”
Section: Introductionmentioning
confidence: 99%