A DFT Study of Electronic Inductive and Resonance Effects of Substituents on Concerted Two‐Proton‐Coupled Electron Transfer Between Catechol Derivatives and Superoxide.
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| Title: | A DFT Study of Electronic Inductive and Resonance Effects of Substituents on Concerted Two‐Proton‐Coupled Electron Transfer Between Catechol Derivatives and Superoxide. |
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| Authors: | Nakayama, Tatsushi1 (AUTHOR) tnakayama@gifu‐pu.ac.jp |
| Source: | Journal of Physical Organic Chemistry. Feb2026, Vol. 39 Issue 2, p1-14. 14p. |
| Subjects: | Inductive effect, Resonance effect, Oxidation-reduction reaction, Computational chemistry, Catechol, Functional groups, Superoxides |
| Abstract: | The development of biomimetic electron transfer catalysts based on proton‐coupled electron transfer (PCET), which is characterized by quinone–hydroquinone π‐conjugation, represents a promising approach for achieving highly efficient artificial energy conversion. Herein, I report a density functional theory (DFT)‐based analysis of the electronic inductive (I) and resonance (R) effects of substituents on concerted two‐proton‐coupled electron transfer (2PCET) between benzene‐1,2‐diol (catechol) derivatives and the superoxide radical anion (O2•−). In this study, I investigated the relationship between the type and number of substituents and their effects on 2PCET using 12 catechol derivatives. Four types of substituents—methyl (+I, +R), chloro (−I, +R), methoxy (−I, +R), and cyano (−I, −R)—were selected in mono‐, di‐, tri‐, and tetra‐substituted forms to isolate and analyze their electronic effects without additional functionalities. My DFT results confirmed that substituent effects selectively enhance either proton or electron transfer along a sequential PCET pathway. Further analysis revealed that the R effect is the primary driving force for concerted 2PCET, where an increasing number of methyl or chloro substituents promotes the reaction, whereas cyano substituents suppress it. The I and R effects influence the electronic properties of the catechol molecule in proportion to the number of substituents. However, free energy calculations indicated kinetic and thermodynamic deviations, suggesting that the substituents directly affected the two hydroxyl groups—the reaction sites of 2PCET—as well as their solvation environment. [ABSTRACT FROM AUTHOR] |
| Copyright of Journal of Physical Organic Chemistry is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | Engineering Source |
| FullText | Text: Availability: 0 |
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| Header | DbId: egs DbLabel: Engineering Source An: 190955647 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: A DFT Study of Electronic Inductive and Resonance Effects of Substituents on Concerted Two‐Proton‐Coupled Electron Transfer Between Catechol Derivatives and Superoxide. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Nakayama%2C+Tatsushi%22">Nakayama, Tatsushi</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> tnakayama@gifu‐pu.ac.jp</i> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Journal+of+Physical+Organic+Chemistry%22">Journal of Physical Organic Chemistry</searchLink>. Feb2026, Vol. 39 Issue 2, p1-14. 14p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Inductive+effect%22">Inductive effect</searchLink><br /><searchLink fieldCode="DE" term="%22Resonance+effect%22">Resonance effect</searchLink><br /><searchLink fieldCode="DE" term="%22Oxidation-reduction+reaction%22">Oxidation-reduction reaction</searchLink><br /><searchLink fieldCode="DE" term="%22Computational+chemistry%22">Computational chemistry</searchLink><br /><searchLink fieldCode="DE" term="%22Catechol%22">Catechol</searchLink><br /><searchLink fieldCode="DE" term="%22Functional+groups%22">Functional groups</searchLink><br /><searchLink fieldCode="DE" term="%22Superoxides%22">Superoxides</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: The development of biomimetic electron transfer catalysts based on proton‐coupled electron transfer (PCET), which is characterized by quinone–hydroquinone π‐conjugation, represents a promising approach for achieving highly efficient artificial energy conversion. Herein, I report a density functional theory (DFT)‐based analysis of the electronic inductive (I) and resonance (R) effects of substituents on concerted two‐proton‐coupled electron transfer (2PCET) between benzene‐1,2‐diol (catechol) derivatives and the superoxide radical anion (O2•−). In this study, I investigated the relationship between the type and number of substituents and their effects on 2PCET using 12 catechol derivatives. Four types of substituents—methyl (+I, +R), chloro (−I, +R), methoxy (−I, +R), and cyano (−I, −R)—were selected in mono‐, di‐, tri‐, and tetra‐substituted forms to isolate and analyze their electronic effects without additional functionalities. My DFT results confirmed that substituent effects selectively enhance either proton or electron transfer along a sequential PCET pathway. Further analysis revealed that the R effect is the primary driving force for concerted 2PCET, where an increasing number of methyl or chloro substituents promotes the reaction, whereas cyano substituents suppress it. The I and R effects influence the electronic properties of the catechol molecule in proportion to the number of substituents. However, free energy calculations indicated kinetic and thermodynamic deviations, suggesting that the substituents directly affected the two hydroxyl groups—the reaction sites of 2PCET—as well as their solvation environment. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Journal of Physical Organic Chemistry is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1002/poc.70064 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 14 StartPage: 1 Subjects: – SubjectFull: Inductive effect Type: general – SubjectFull: Resonance effect Type: general – SubjectFull: Oxidation-reduction reaction Type: general – SubjectFull: Computational chemistry Type: general – SubjectFull: Catechol Type: general – SubjectFull: Functional groups Type: general – SubjectFull: Superoxides Type: general Titles: – TitleFull: A DFT Study of Electronic Inductive and Resonance Effects of Substituents on Concerted Two‐Proton‐Coupled Electron Transfer Between Catechol Derivatives and Superoxide. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Nakayama, Tatsushi IsPartOfRelationships: – BibEntity: Dates: – D: 01 M: 02 Text: Feb2026 Type: published Y: 2026 Identifiers: – Type: issn-print Value: 08943230 Numbering: – Type: volume Value: 39 – Type: issue Value: 2 Titles: – TitleFull: Journal of Physical Organic Chemistry Type: main |
| ResultId | 1 |
