Prediction of Kinetic Isotope Effects for Various Hydride Transfer Reactions Using a New Kinetic Model

Shen, Guang‐Bin; Xia, Ke; Li, Xiu-Tao; Li, Junling; Fu, Yan‐Hua; Yuan, Lin; Zhu, Xiao‐Qing

doi:10.1021/acs.jpca.5b10135

Cited by 41 publications

(62 citation statements)

References 51 publications

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“…aExperimental activation free energies directly derived from refs (18)(20), and (36) using Eyring equation. 39 bComputational activation free energies by using different methods to compute the gas-phase electronic energy (method 1: M06-2X-D3/def2-TZVPP; method 2: M06-2X-D3/def2-QZVP; method 3: M06-2X-D3/MG3S; method 4: M06-2X/def2-TZVPP; method 5: B3LYP-D3(BJ)/def2-TZVPP; and method 6: BMK-D3(BJ)/def2-TZVPP).cMAD, mean absolute deviation; RMSD, root-mean-square deviation.…”

Section: Resultsmentioning

confidence: 99%

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Theoretical Prediction of Activation Free Energies of Various Hydride Self-Exchange Reactions in Acetonitrile at 298 K

Yang

Zhu

2018

ACS Omega

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Hydride transfer reactions are very important chemical reactions in organic chemistry. It has been a chemist’s dream to predict the rate constants of hydride transfer reactions by only using the physical parameters of the reactants. To realize this dream, we have developed a kinetic equation (Zhu equation) in our previous papers to predict the activation free energies of various chemical reactions using the activation free energies of the corresponding self-exchange reactions and the related bond dissociation energies or redox potentials of the reactants. Because the activation free energy of the hydride self-exchange reaction is difficult to measure using the experimental method, in this study, the activation free energies of 159 hydride self-exchange reactions in acetonitrile at 298 K were systematically computed using an accurately benchmarked density functional theory method with a precision of 1.1 kcal mol –1 . The results show that the range of the activation free energies of the 159 hydride self-exchange reactions is from 16.1 to 46.6 kcal mol –1 . The activation free energies of 25 122 hydride transfer reactions in acetonitrile at 298 K can be estimated using the activation free energies of the 159 hydride self-exchange reactions and the corresponding heterolytic bond dissociation free energies of the reactants. The effects of the heteroatom, substituent, and aromaticity on the activation free energies of hydride self-exchange reactions were examined. The results show that heteroatoms, substituents at the reaction center, and the aromaticity of reactants, all have remarkable effects on the activation free energy of hydride self-exchange reactions. All kinetic information provided in this work on the hydride self-exchange reactions in acetonitrile at 298 K should be very useful in chemical labs and chemical industry.

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Section: Resultsmentioning

confidence: 99%

“…aExperimental activation free energies directly derived from refs (18)(20), and (36) using Eyring equation. 39 …”

Section: Resultsmentioning

confidence: 99%

Theoretical Prediction of Activation Free Energies of Various Hydride Self-Exchange Reactions in Acetonitrile at 298 K

Yang

Zhu

2018

ACS Omega

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Section: Definition Of the Thermo‐kinetic Parametermentioning

confidence: 99%

“…In our previous paper, we reported a new kinetic equation (eq 3) to describe the quantitative dependence of Δ G ≠ XH/Y on Δ G o XH/Y for chemical reactions. The new kinetic equation (eq 3) was named as Zhu's kinetic equation . The validity of eq 3 has received strong verification by safely predicting the activation free energy and the corresponding kinetic isotopic effect values of various hydride transfer reactions in acetonitrile at 298 K …”

Section: Definition Of the Thermo‐kinetic Parametermentioning

confidence: 99%

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Realization of Quantitative Estimation for Reaction Rate Constants Using only One Physical Parameter for Each Reactant

Shen

et al. 2017

ChemistrySelect

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In this present paper, a new physical parameter (named as thermo‐kinetic parameter) of reactants was defined according to Zhu's kinetic equation, which can be used to quantitatively estimate activation free energy of various chemical reactions. In order to test the actual application of the thermo‐kinetic parameter of reactants, the thermo‐kinetic parameter values of 109 hydrogen atom donors and 109 hydrogen atom acceptors in acetonitrile at 298 K were determined using experimental methods and the rate constants of 5886 hydrogen atom transfer reactions in acetonitrile at 298 K were quantitatively estimated only using the thermo‐kinetic parameter values of the 109 hydrogen atom donors and the 109 hydrogen atom acceptors in acetonitrile at 298 K. The reliabilities of the estimations were verified. Physical meanings and affecting factors of the thermo‐kinetic parameter were elucidated and examined, respectively. The most significant contribution of this paper is to realize the chemists’ dream for a century that the reaction rate constants can be quantitatively estimated using only one physical parameter for each reactant.

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Deuterium‐ und tritiummarkierte Verbindungen: Anwendungen in den modernen Biowissenschaften

Atzrodt¹,

Derdau²,

Kerr

et al. 2018

Angewandte Chemie

108

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Wasserstoffisotope sind einzigartige Werkzeuge zur Identifizierung und Erforschung biologischer oder chemischer Vorgänge. Wasserstoffisotopenmarkierungen erlauben den spurlosen und direkten Einbau einer zusätzlichen Masseneinheit oder eines radioaktiven Markers in ein organisches Molekül, und dies praktisch ohne Änderungen der chemischen Struktur, der physikalischen Eigenschaften oder der biologischen Aktivität. Die Verwendung von deuteriummarkierten Isotopologen zur Untersuchung der spezifischen massenspektrometrischen (MS) Muster, die von Gemischen biologisch relevanter Moleküle hervorgerufen werden, ermöglicht eine drastische Vereinfachung der Analyse. Solche Methoden ermöglichen nun tiefe Einblicke in einen großen, kontinuierlich anwachsenden Bereich von Anwendungen in den Biowissenschaften und darüber hinaus. Speziell Tritium (3H) wird zunehmend eingesetzt, insbesondere in der pharmazeutischen Wirkstoffsuche. Aufwand und Kosten der Synthese markierter Verbindungen werden durch die hohe Empfindlichkeit der Analyse und hohe Zuverlässigkeit der erhaltenen Daten mehr als ausgeglichen. In diesem Aufsatz werden Fortschritte bei der Verwendung von Wasserstoffisotopen in den Biowissenschaften beschrieben.

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Prediction of Kinetic Isotope Effects for Various Hydride Transfer Reactions Using a New Kinetic Model

Cited by 41 publications

References 51 publications

Theoretical Prediction of Activation Free Energies of Various Hydride Self-Exchange Reactions in Acetonitrile at 298 K

Theoretical Prediction of Activation Free Energies of Various Hydride Self-Exchange Reactions in Acetonitrile at 298 K

Realization of Quantitative Estimation for Reaction Rate Constants Using only One Physical Parameter for Each Reactant

Deuterium‐ und tritiummarkierte Verbindungen: Anwendungen in den modernen Biowissenschaften

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