Quantum Chemical Analyses of BH4− and BH3OH− Hydride Transfers to CO2 in Aqueous Solution with Potentials of Mean Force

Groenenboom, Mitchell C.; Keith, John A.

doi:10.1002/cphc.201700608

Cited by 7 publications

(1 citation statement)

References 38 publications

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“…− is known to act as either a hydride transfer 37,31 or a hydrogen atom transfer (HAT) reagent. 38 Hence, the reaction can be initiated by a proton, hydrogen atom, or hydride transfer (Figure 2).…”

Section: Introductionmentioning

confidence: 99%

DFT Study on Fe(IV)-Peroxo Formation and H Atom Transfer Triggered O₂ Activation by NiFe Complex

et al. 2018

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The mechanism for dioxygen activation using the biomimetic model complex of [NiFe]-hydrogenase, [NiLFe(η5-C5Me5)]+ [L = N,N′-diethyl-3,7-diazanonane-1,9-dithiolato] was established using density functional theory (DFT) and artificial force-induced reaction (AFIR) methods. Our computational results suggest that O2 binds to the FeII center in an end-on fashion and forms a high-valent iron complex, NiFe–peroxo (NiIIFeIV(η2-O2)), which has been experimentally observed. The O–O bond cleavage occurs in the presence of borohydride (BH4 –) through hydrogen atom transfer (HAT). Once the HAT occurs, the generated BH3 radical anion (BH3 •–) binds to the terminal oxygen of NiFe–OOH, giving rise to BH3OH– and NiIIFeIVO. The second HAT from BH4 – to the oxygen of NiIIFeIVO leads to BH3OH– and Fe-reduced NiIIFeII complex. Importantly, the dioxygen activation is triggered by HAT, not by proton transfer or hydride transfer. The O2 is activated by the Fe center, and the oxidation state of Fe varies during the process, while the oxidation state of Ni is conserved. These mechanistic insights into O2 activation are essential in understanding the formation of the inactive state and reactivation process in hydrogenase.

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Section: Introductionmentioning

confidence: 99%

DFT Study on Fe(IV)-Peroxo Formation and H Atom Transfer Triggered O₂ Activation by NiFe Complex

et al. 2018

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Advances and challenges in modeling solvated reaction mechanisms for renewable fuels and chemicals

Basdogan

Maldonado

Keith

2019

WIREs Comput Mol Sci

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We provide a critical overview of progress and challenges in computationally modeling multistep reaction mechanisms relevant for catalysis and electrocatalysis.We first discuss how the chemical and materials space of energetically efficient catalysis can be explored with computational chemistry. Since reactions for renewable energy catalysis can involve acid-base chemistry and/or ions under aqueous conditions, we then summarize how solvation can be modeled with quantum chemistry schemes using implicit, mixed implicit/explicit, and fully explicit solvation modeling. We will discuss the insights (and limitations) of these solvation models primarily through the scope of understanding CO 2 reduction reaction mechanisms, but these will also be applicable for future work elucidating other reaction mechanisms of critical importance for human sustainability such as H 2 O oxidation and N 2 reduction. This article is categorized under: Structure and Mechanism > Reaction Mechanisms and Catalysis K E Y W O R D S cluster-continuum, CO 2 reduction, mixed implicit/explicit, phase diagrams, Pourbaix diagrams, solvation modeling

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Combining experimental and theoretical insights for reduction of CO2 to multi-carbon compounds

et al. 2022

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The electrochemical reduction of carbon dioxide is a promising method for both recycling of atmospheric CO2 and storing renewably produced electrical energy in stable chemical bonds. In this paper, we review the current challenges within this promising area of research. Here we provide an overview of key findings from the perspective of improving the selectivity of reduction products, to serve as a contextual foundation from which a firmer understanding of the field can be built. Additionally, we discuss recent innovations in the development of catalytic materials selective toward C3 and liquid products. Through this, we form a basis from which key mechanisms into C3 products may be further examined. Carbon–carbon (C–C) bond formation provides a key step in the reduction of CO2 to energy dense and high value fuels. Here we demonstrate how variations in catalytic surface morphology and reaction kinetics influence the formation of multi-carbon products through their impact on the formation of C–C bonds. Finally, we discuss recent developments in the techniques used to characterise and model novel electrocatalysts. Through these insights, we hope to provide the reader with a perspective of both the rapid progress of the field of electrocatalysis, as well as offering a concise overview of the challenges faced by researchers within this rapidly developing field of research.

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Quantum Chemical Analyses of BH₄⁻ and BH₃OH⁻ Hydride Transfers to CO₂ in Aqueous Solution with Potentials of Mean Force

Cited by 7 publications

References 38 publications

DFT Study on Fe(IV)-Peroxo Formation and H Atom Transfer Triggered O₂ Activation by NiFe Complex

DFT Study on Fe(IV)-Peroxo Formation and H Atom Transfer Triggered O₂ Activation by NiFe Complex

Advances and challenges in modeling solvated reaction mechanisms for renewable fuels and chemicals

Combining experimental and theoretical insights for reduction of CO2 to multi-carbon compounds

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Quantum Chemical Analyses of BH4− and BH3OH− Hydride Transfers to CO2 in Aqueous Solution with Potentials of Mean Force

Cited by 7 publications

References 38 publications

DFT Study on Fe(IV)-Peroxo Formation and H Atom Transfer Triggered O2 Activation by NiFe Complex

DFT Study on Fe(IV)-Peroxo Formation and H Atom Transfer Triggered O2 Activation by NiFe Complex

Advances and challenges in modeling solvated reaction mechanisms for renewable fuels and chemicals

Combining experimental and theoretical insights for reduction of CO2 to multi-carbon compounds

Contact Info

Product

Resources

About

Quantum Chemical Analyses of BH₄⁻ and BH₃OH⁻ Hydride Transfers to CO₂ in Aqueous Solution with Potentials of Mean Force

DFT Study on Fe(IV)-Peroxo Formation and H Atom Transfer Triggered O₂ Activation by NiFe Complex

DFT Study on Fe(IV)-Peroxo Formation and H Atom Transfer Triggered O₂ Activation by NiFe Complex