The Strongest Acid: Protonation of Carbon Dioxide

Cummings, Steven P.; Hratchian, Hrant P.; Reed, Christopher A.

doi:10.1002/ange.201509425

Cited by 7 publications

(2 citation statements)

References 52 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The latter is ruled out because direct protonation of CO 2 is thermodynamically unfavorable under the neutral reaction conditions. 59 Within the theory of PCET, it is wellestablished 60 that an enabling feature of a CPET pathway is that it lowers the energy barrier associated with this elementary process if either the PT or ET step exhibits a large energy penalty, that is, the free energy change for PT (pK a ) or ET (potential) is prohibitively high. Recent work also demonstrated how PCET can be exploited in photoredox processes, where ET is enabled by a photoreductant, permitting light-driven reactivity otherwise inaccessible by the redox potentials of using commonly available photoredox catalysts.…”

Section: Controlling Electrosynthetic Reaction Selectivity Via Contro...mentioning

confidence: 99%

“…CO 2 electroreduction can proceed via a sequential electron transfer‐ proton transfer (ET‐PT, across then down via intermediate 1 , Figure 2a) mechanism, a concerted proton electron transfer (CPET, diagonal in Figure 2a) mechanism, or a sequential proton transfer‐electron transfer (PT‐ET) mechanism. The latter is ruled out because direct protonation of CO 2 is thermodynamically unfavorable under the neutral reaction conditions 59 . Within the theory of PCET, it is well‐established 60 that an enabling feature of a CPET pathway is that it lowers the energy barrier associated with this elementary process if either the PT or ET step exhibits a large energy penalty, that is, the free energy change for PT (pK a ) or ET (potential) is prohibitively high.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

The interface is a tunable dimension in electricity‐driven organic synthesis

Wuttig

Toste

2021

Natural Sciences

View full text Add to dashboard Cite

Predictive control over the selectivity outcome of an organic synthetic method is an essential hallmark of reaction success. Electricity‐driven synthesis offers a reemerging approach to facilitate the design of reaction sequences toward increased molecular complexity. In addition to the desirable sustainability features of electroorganic processes, the inherent interfacial nature of electrochemical systems present unique opportunities to tune reaction selectivity. To illustrate this feature, we outline examples of mechanism‐guided interfacial control over CO2 electroreduction selectivity; a well‐studied and instructive electrochemical process with multiple reduction products that are thermodynamically accessible. These studies reveal how controlled proton delivery to the electrode surface and substrate electrosorption with the electrode dictate reaction selectivity. We describe and compare simple, yet salient, examples from the electroorganic literature, where we postulate that similar effects predominate the observed reactivity. This perspective highlights how the interface serves as a tunable dimension in electrochemical processes and delineates unique tools to study, manipulate, and achieve reaction selectivity in electricity‐driven organic synthesis. KEY POINTS Electricity‐driven synthesis enables chemical and industrial communities to contribute to sustainability goals. Electricity‐driven processes occur at phase boundaries, thus unveiling their molecular‐level roadmaps involves the synergistic study of materials, interfacial, and molecular science. Bridging concepts that transcend the topical nature of two electricity‐driven processes—CO2 reduction and electroorganic synthesis—reveals tools to manipulate reaction selectivity.

show abstract

Section: Controlling Electrosynthetic Reaction Selectivity Via Contro...mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The interface is a tunable dimension in electricity‐driven organic synthesis

Wuttig

Toste

2021

Natural Sciences

View full text Add to dashboard Cite

show abstract

Features of Protonation of the Simplest Weakly Basic Molecules, SO₂, CO, N₂O, CO₂, and Others by Solid Carborane Superacids

Stoyanov

Stoyanova

2018

Angewandte Chemie

View full text Add to dashboard Cite

An experimental study on protonation of simple weakly basic molecules (L) by the strongest solid superacid, H(CHB 11 F 11 ), showed that basicity of SO 2 is high enough (during attachment to the acidic Hatoms at partial pressure of 1atm) to break the bridged H-bonds of the polymeric acid and to form am ixture of solid mono-LH + ···An À ,a nd disolvates, L À H + À L. With ad ecrease in the basicity of L = CO (via C), N 2 O, and CO (via O), only proton monosolvates are formed, which approach LÀH + ÀAn À species with convergence of the strengths of bridged H-bonds.The molecules with the weakest basicity,such as CO 2 and weaker,when attached to the proton, cannot break the bridged H-bond of the polymeric superacid, and the interaction stops at stage of physical adsorption. It is shown here that under the conditions of acid monomerization, it is possible to protonate such weak bases as CO 2 ,N 2 ,and Xe.

show abstract

Features of Protonation of the Simplest Weakly Basic Molecules, SO₂, CO, N₂O, CO₂, and Others by Solid Carborane Superacids

Stoyanov

Stoyanova

2018

Angew Chem Int Ed

View full text Add to dashboard Cite

An experimental study on protonation of simple weakly basic molecules (L) by the strongest solid superacid, H(CHB F ), showed that basicity of SO is high enough (during attachment to the acidic H atoms at partial pressure of 1 atm) to break the bridged H-bonds of the polymeric acid and to form a mixture of solid mono- LH ⋅⋅⋅An , and disolvates, L-H -L. With a decrease in the basicity of L=CO (via C), N O, and CO (via O), only proton monosolvates are formed, which approach L-H -An species with convergence of the strengths of bridged H-bonds. The molecules with the weakest basicity, such as CO and weaker, when attached to the proton, cannot break the bridged H-bond of the polymeric superacid, and the interaction stops at stage of physical adsorption. It is shown here that under the conditions of acid monomerization, it is possible to protonate such weak bases as CO , N , and Xe.

show abstract

The Strongest Acid: Protonation of Carbon Dioxide

Cited by 7 publications

References 52 publications

The interface is a tunable dimension in electricity‐driven organic synthesis

The interface is a tunable dimension in electricity‐driven organic synthesis

Features of Protonation of the Simplest Weakly Basic Molecules, SO₂, CO, N₂O, CO₂, and Others by Solid Carborane Superacids

Features of Protonation of the Simplest Weakly Basic Molecules, SO₂, CO, N₂O, CO₂, and Others by Solid Carborane Superacids

Contact Info

Product

Resources

About

The Strongest Acid: Protonation of Carbon Dioxide

Cited by 7 publications

References 52 publications

The interface is a tunable dimension in electricity‐driven organic synthesis

The interface is a tunable dimension in electricity‐driven organic synthesis

Features of Protonation of the Simplest Weakly Basic Molecules, SO2, CO, N2O, CO2, and Others by Solid Carborane Superacids

Features of Protonation of the Simplest Weakly Basic Molecules, SO2, CO, N2O, CO2, and Others by Solid Carborane Superacids

Contact Info

Product

Resources

About

Features of Protonation of the Simplest Weakly Basic Molecules, SO₂, CO, N₂O, CO₂, and Others by Solid Carborane Superacids

Features of Protonation of the Simplest Weakly Basic Molecules, SO₂, CO, N₂O, CO₂, and Others by Solid Carborane Superacids