An electrochemical methodology for the cyclic CO2 “catch and release”. The role of the electrogenerated N-heterocyclic carbene in BMIm-BF4

Feroci, Marta; Chiarotto, Isabella; Forte, Gianpiero; Inesi, Achille

doi:10.1016/j.jcou.2013.07.002

Cited by 29 publications

(32 citation statements)

References 55 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Moreover, this peculiar anodic peak is present both in pre-electrolyzed BMImBF4 (E < −1.9 V) and in DBU-BMImBF4 solution, being DBU a strong organic base (1,8-diazabicyclo[5.4.0]undec-7-ene). Therefore, NHC can be generated by both cathodic reduction and chemical deprotonation of NHCH + [31]. The NHC oxidation peak current increases on increasing the concentration of NHC, i.e., on increasing the concentration of added DBU or of the number of Faradays consumed during the electrolysis of BMImBF4, as expected.…”

Section: Electrodic Activity Of the System Nhch + /Nhcsupporting

confidence: 70%

“…This system is able to catch and release CO 2 cyclically and in mild conditions. After a single electrolysis, in a series of 10 cycles the solution (electrogenerated NHC in imidazolium salt as solvent) was able to catch and release 4 mol of CO 2 per Faradays consumed during the electrolysis [31]. These investigations, extended to different ionic liquids BMImX, proved that the rate of CO 2 capture is affected by the nature of the counter ion X − [39].…”

mentioning

confidence: 89%

“…More recently, the voltammetric behavior of neat azolium salts (imidazolium-, triazolium-, and thiazolium-based) or of their solutions (N,N-dimethylformamide (DMF), and MeCN as solvents) was reconsidered [28][29][30][31][32]. The NHCH + reduction and NHC oxidation potentials are obviously dependent on structure of the azolium cation, of the counter-ion, the presence and the nature of the solvent, and the electrode material ( Figure 5).…”

Section: Electrodic Activity Of the System Nhch + /Nhcmentioning

confidence: 99%

“…In fact, the peak current decreases on increasing the value of the reversal potential from −2.5 to −1.9 V, according to a different pilling up of the electroactive species (NHC). No oxidation peak is present in the voltammogram if the value of the reversal potential is >−1.8 V (Figure 6) [31].…”

Section: Electrodic Activity Of the System Nhch + /Nhcmentioning

confidence: 99%

“…Recently, papers described the electrochemical synthesis of NHC-CO 2 adducts for the CO 2 catch and release [29,31,39]. A simple electrolysis of neat liquid imidazolium salts (e.g., 1-butyl-3-methyl-1H-imidazolium tetrafluoroborate) generated NHC in the catholyte and, after carbon dioxide bubbling, the NHC-CO 2 adduct.…”

mentioning

confidence: 99%

See 4 more Smart Citations

Advances in the Knowledge of N-Heterocyclic Carbenes Properties. The Backing of the Electrochemical Investigation

2016

Self Cite

View full text Add to dashboard Cite

In the last twenty years, N-heterocyclic carbenes (NHCs) have acquired considerable popularity as ligands for transition metals, organocatalysts and in metal-free polymer synthesis. NHCs are generally derived from azolium based salts NHCH+X− by deprotonation or reduction (chemical or electrochemical) of NHCH+. The extensive knowledge of the physicochemical properties of NHCH+/NHC system could help to select the conditions (scaffold of NHC, nature of the counter-ion X−, solvent, etc.) to enhance the catalytic power of NHC in a synthesis. The electrochemical behavior of NHCH+/NHC system, in the absence and in the presence of solvent, was extensively discussed. The cathodic reduction of NHCH+ to NHC and the anodic oxidation of NHC, and the related effect of the scaffold, solvent, and electrodic material were emphasized. The electrochemical investigations allow acquiring further knowledge as regards the stability of NHC, the acidic and nucleophilic properties of NHCH+/NHC system, the reactivity of NHC versus carbon dioxide and the effect of the hydrogen bond on the catalytic efficiency of NHC. The question of the spontaneous or induced formation of NHC from particular ionic liquids was reconsidered via voltammetric analysis. The results suggested by the classical and the electrochemical methodologies were compared and discussed.

show abstract

Section: Electrodic Activity Of the System Nhch + /Nhcsupporting

confidence: 70%

mentioning

confidence: 89%

Section: Electrodic Activity Of the System Nhch + /Nhcmentioning

confidence: 99%

Section: Electrodic Activity Of the System Nhch + /Nhcmentioning

confidence: 99%

mentioning

confidence: 99%

See 3 more Smart Citations

Advances in the Knowledge of N-Heterocyclic Carbenes Properties. The Backing of the Electrochemical Investigation

2016

Self Cite

View full text Add to dashboard Cite

show abstract

The Chemistry of Azolium‐Carboxylate Zwitterions and Related Compounds: a Survey of the Years 2009–2020

Delaude

2020

Adv Synth Catal

View full text Add to dashboard Cite

This review highlights the most significant advances that were accomplished in the chemistry of azolium‐carboxylate betaines within the years 2009–2020. Whenever needed, prior, seminal achievements are also briefly recalled to help put recent developments in a broader perspective. The compounds under scrutiny are zwitterions obtained upon nucleophilic addition of N‐heterocyclic carbenes (NHCs) onto carbon dioxide. We first present an overview of the various synthetic paths that give access to these inner salts before discussing their stability. The main part of this report then summarizes the numerous applications relying on NHC ⋅ CO2 zwitterions employed either in stoichiometric or catalytic proportions in the fields of organometallic chemistry and homogeneous catalysis, organic synthesis and organocatalysis, polymer chemistry, and materials science. A particular emphasis is placed on the endeavors devoted to trap carbon dioxide and to convert this greenhouse gas into valuable chemicals via the intermediacy of NHC ⋅ CO2 zwitterions. Whenever available, mechanistic considerations that help assess the pivotal role played by these species in CO2 activation are discussed. Because of their close relationship with azolium‐carboxylate betaines, azolium hydrogencarbonate salts and azolium‐methylenecarboxylate zwitterions resulting from the addition of carbon dioxide onto N‐heterocyclic olefins (NHOs) are included in this survey, which also covers the reactivity of carbon monoxide toward NHCs and related carbene species.magnified image

show abstract

Electrochemical Generation of N‐Heterocyclic Carbenes for Use in Synthesis and Catalysis

et al. 2021

View full text Add to dashboard Cite

The electrochemical generation of N‐heterocyclic carbenes (NHCs) offers a mild and selective alternative to traditional synthetic methods that usually rely on strong bases and air‐sensitive materials. The use of electrons as reagents results in an efficient and clean synthesis that enables the direct use of NHCs in various applications. Herein, the use of electrogenerated NHCs in organocatalysis, synthesis and organometallic chemistry is explored.

show abstract

An electrochemical methodology for the cyclic CO2 “catch and release”. The role of the electrogenerated N-heterocyclic carbene in BMIm-BF4

Cited by 29 publications

References 55 publications

Advances in the Knowledge of N-Heterocyclic Carbenes Properties. The Backing of the Electrochemical Investigation

Advances in the Knowledge of N-Heterocyclic Carbenes Properties. The Backing of the Electrochemical Investigation

The Chemistry of Azolium‐Carboxylate Zwitterions and Related Compounds: a Survey of the Years 2009–2020

Electrochemical Generation of N‐Heterocyclic Carbenes for Use in Synthesis and Catalysis

Contact Info

Product

Resources

About