Hydrogen Tunneling in Catalytic Hydrolysis and Alcoholysis of Silanes

Almenara, Naroa; Garralda, María A.; López, Xabier; Matxain, Jon M.; Freixa, Zoraida; Huertos, Miguel A.

doi:10.1002/anie.202204558

Cited by 13 publications

(8 citation statements)

References 65 publications

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“…The last example in this section discusses the participation of hydrogen tunneling in the hydrolysis of triethylsilane catalyzed by a cationic iridium(III) complex (Figure 6e). [10] Experimentally a significantly large value of KIE (KIE=346) was obtained. Moreover, the temperature dependence of KIE was also observed [ A (H) /A (D)=0.0004 and ( E a (D) –E a (H))=8.1 kcal mol −1 .…”

Section: Hydrogen Tunneling With Participation Of Metal Complexesmentioning

confidence: 94%

Hydrogen Tunneling in Stoichiometric and Catalytic Reactions involving Transition Metals

Matxain,

Huertos

2023

ChemCatChem

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Hydrogen tunneling is a type of quantum tunneling in which a hydrogen atom passes through a potential barrier without reaching the transition state governed by classical mechanics. The participation of hydrogen tunneling in a chemical reaction (stoichiometric or catalytic) can result in the formation of products that without this phenomenon would be impossible to achieve or would be formed in a very slow way. This concept paper aims to review some of the most representative examples of transition‐metal mediated chemical reactions involving hydrogen tunneling. The experimental tools to determine the possibility of the participation of quantum tunneling in a chemical reaction are presented. In addition, the theoretical methods that have been developed to calculate the effect of quantum tunneling on chemical reactions are discussed. Finally, from a personal perspective, the steps to be taken in order to predict and implement this phenomenon are proposed.

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Section: Hydrogen Tunneling With Participation Of Metal Complexesmentioning

confidence: 94%

Hydrogen Tunneling in Stoichiometric and Catalytic Reactions involving Transition Metals

Matxain,

Huertos

2023

ChemCatChem

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“…Of course, modern developments of transition state theory (TST) take tunneling fully into account, − but in contrast to the notion of barrier heights, barrier widths play essentially no role in the qualitative description of chemical reactions. As QMT has been recognized as being more common than typically assumed, one cannot argue that it is likely to be of minor importance for typical chemical reactions. − In particular, the barrier width reduction was found to be directly linked to the increase in the rates of QMT processes . Therefore, just as there is a systematic modulation of the barrier height, the barrier width also deserves a similarly systematic treatment in order to acquire a holistic understanding of chemical reactivity.…”

Section: Introductionmentioning

confidence: 99%

The Intrinsic Barrier Width and Its Role in Chemical Reactivity

Qiu,

Schreiner

2023

ACS Cent. Sci.

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Chemical reactions are in virtually all cases understood and explained on the basis of depicting the molecular potential energy landscape, i.e., the change in atomic positions vs the free-energy change. With such landscapes, the features of the reaction barriers solely determine chemical reactivities. The Marcus dissection of the barrier height (activation energy) on such a potential into the thermodynamically independent (intrinsic) and the thermodynamically dependent (Bell–Evans–Polanyi) contributions successfully models the interplay of reaction rate and driving force. This has led to the well-known and ubiquitously used reactivity paradigm of “kinetic versus thermodynamic control”. However, an analogous dissection concept regarding the barrier width is absent. Here we define and outline the concept of intrinsic barrier width and the driving force effect on the barrier width and report experimental as well as theoretical studies to demonstrate their distinct roles. We present the idea of changing the barrier widths of conformational isomerizations of some simple aromatic carboxylic acids as models and use quantum mechanical tunneling (QMT) half-lives as a read-out for these changes because QMT is particularly sensitive to barrier widths. We demonstrate the distinct roles of the intrinsic and the thermodynamic contributions of the barrier width on QMT half-lives. This sheds light on resolving conflicting trends in chemical reactivities where barrier widths are relevant and allows us to draw some important conclusions about the general relevance of barrier widths, their qualitative definition, and the consequences for more complete descriptions of chemical reactions.

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“…As QMT has been recognized as being more common than typically assumed, 10 one cannot argue that it is likely to be of minor importance for typical chemical reactions. [11][12][13][14][15][16][17][18][19][20][21][22][23][24] Every transfer of light particles such as hydrogens, protons, and hydrides will involve QMT to varying degrees and this will be readily noticeable in the reaction rates.…”

Section: Introductionmentioning

confidence: 99%

The Intrinsic Barrier Width and its Role in Chemical Reactivity

Qiu

Schreiner

2023

Preprint

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The Marcus dissection of the Gibbs activation energy (barrier height) into intrinsic and thermodynamic contributions, which successfully models the interplay of rate and driving force, has led to a crucial general phenomenological consequence: the well-known two reactivity paradigms of “kinetic versus thermodynamic control”. However, concepts analogous to the Marcus’ dissection for barrier widths are absent. Here we define and outline the barrier-width- counterpart of the Marcus dissection: the concept of intrinsic barrier width and driving force effect on the barrier width, and report experimental as well as theoretical studies to demonstrate their distinct roles. We present the idea of changing the barrier widths of conformational isomerizations of some simple aromatic carboxylic acids as models and use quantum mechanical tunneling (QMT) half-lives as a read-out for these changes. This sheds light on resolving conflicting trends in chemical reactivities where barrier widths are relevant, and allows us to draw some important conclusions about the general relevance of barrier widths, their qualitative definition, and the consequences for more complete descriptions of chemical reactions based on one-dimensional reaction coordinates.

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Hydrogen Tunneling in Catalytic Hydrolysis and Alcoholysis of Silanes

Cited by 13 publications

References 65 publications

Hydrogen Tunneling in Stoichiometric and Catalytic Reactions involving Transition Metals

Hydrogen Tunneling in Stoichiometric and Catalytic Reactions involving Transition Metals

The Intrinsic Barrier Width and Its Role in Chemical Reactivity

The Intrinsic Barrier Width and its Role in Chemical Reactivity

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