ACS Publications. Most Trusted. Most Cited. Most Read
My Activity

Figure 1Loading Img

Redox Chemistry of Selenenic Acids and the Insight It Brings on Transition State Geometry in the Reactions of Peroxyl Radicals

View Author Information
Department of Chemistry, University of Ottawa, Ottawa, Ontario K1N 6N5, Canada
Department of Chemistry “G. Ciamician”, University of Bologna, I-40126 Bologna, Italy
Cite this: J. Am. Chem. Soc. 2014, 136, 4, 1570–1578
Publication Date (Web):January 2, 2014
Copyright © 2014 American Chemical Society

    Article Views





    Other access options
    Supporting Info (1)»


    Abstract Image

    The redox chemistry of selenenic acids has been explored for the first time using a persistent selenenic acid, 9-triptyceneselenenic acid (RSeOH), and the results have been compared with those we recently obtained with its lighter chalcogen analogue, 9-triptycenesulfenic acid (RSOH). Specifically, the selenenyl radical was characterized by EPR spectroscopy and equilibrated with a phenoxyl radical of known stability in order to determine the O–H bond dissociation enthalpy of RSeOH (80.9 ± 0.8 kcal/mol): ca. 9 kcal/mol stronger than in RSOH. Kinetic measurements of the reactions of RSeOH with peroxyl radicals demonstrate that it readily undergoes H-atom transfer reactions (e.g., k = 1.7 × 105 M–1 s–1 in PhCl), which are subject to kinetic solvent effects and kinetic isotope effects similar to RSOH and other good H-atom donors. Interestingly, the rate constants for these reactions are only 18- and 5-fold smaller than those measured for RSOH in PhCl and CH3CN, respectively, despite being 9 kcal/mol less exothermic for RSeOH. IR spectroscopic studies demonstrate that RSeOH is less H-bond acidic than RSOH, accounting for these solvent effects and enabling estimates of the pKas in RSeOH and RSOH of ca. 15 and 10, respectively. Calculations suggest that the TS structures for these reactions have significant charge transfer between the chalcogen atom and the internal oxygen atom of the peroxyl radical, which is nominally better for the more polarizable selenenic acid. The higher than expected reactivity of RSeOH toward peroxyl radicals is the strongest experimental evidence to date for charge transfer/secondary orbital interactions in the reactions of peroxyl radicals with good H-atom donors.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.


    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Supporting Information

    Jump To

    NMR spectra of new compounds, representative voltammograms, Cartesian coordinates, and energies of stationary points determined by computation. This material is available free of charge via the Internet at

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

    Cited By

    This article is cited by 47 publications.

    1. Liliya T. Sahharova, Julia V. Burykina, Alexander Yu. Kostyukovich, Dmitry B. Eremin, Daniil A. Boiko, Artem N. Fakhrutdinov, Valentine P. Ananikov. Expanding the Role of Dimeric Species: On-Cycle Involvement, Improved Stability, and Control of Stereo-Specificity. A Case Study of Atom-Economic Catalytic Hydrothiolation. ACS Catalysis 2023, 13 (6) , 3591-3604.
    2. Melodie Mallais, Carly S. Hanson, Melanie Giray, Derek A. Pratt. General Approach to Identify, Assess, and Characterize Inhibitors of Lipid Peroxidation and Associated Cell Death. ACS Chemical Biology 2023, 18 (3) , 561-571.
    3. Ryosuke Masuda, Ryutaro Kimura, Takafumi Karasaki, Shohei Sase, Kei Goto. Modeling the Catalytic Cycle of Glutathione Peroxidase by Nuclear Magnetic Resonance Spectroscopic Analysis of Selenocysteine Selenenic Acids. Journal of the American Chemical Society 2021, 143 (17) , 6345-6350.
    4. Liliya T. Sahharova, Evgeniy G. Gordeev, Dmitry B. Eremin, Valentine P. Ananikov. Pd-Catalyzed Synthesis of Densely Functionalized Cyclopropyl Vinyl Sulfides Reveals the Origin of High Selectivity in a Fundamental Alkyne Insertion Step. ACS Catalysis 2020, 10 (17) , 9872-9888.
    5. Jia-Fei Poon, Derek A. Pratt. Recent Insights on Hydrogen Atom Transfer in the Inhibition of Hydrocarbon Autoxidation. Accounts of Chemical Research 2018, 51 (9) , 1996-2005.
    6. Andrea Baschieri, Luca Valgimigli, Simone Gabbanini, Gino A. DiLabio, Eduardo Romero-Montalvo, Riccardo Amorati. Extremely Fast Hydrogen Atom Transfer between Nitroxides and HOO· Radicals and Implication for Catalytic Coantioxidant Systems. Journal of the American Chemical Society 2018, 140 (32) , 10354-10362.
    7. Jian Xu, Zhuang Wu, Huabin Wan, Guohai Deng, Bo Lu, André K. Eckhardt, Peter R. Schreiner, Tarek Trabelsi, Joseph S. Francisco, Xiaoqing Zeng. Phenylsulfinyl Radical: Gas-Phase Generation, Photoisomerization, and Oxidation. Journal of the American Chemical Society 2018, 140 (31) , 9972-9978.
    8. Zhuang Wu, Ruijuan Feng, Jian Xu, Yan Lu, Bo Lu, Tao Yang, Gernot Frenking, Tarek Trabelsi, Joseph S. Francisco, and Xiaoqing Zeng . Photoinduced Sulfur–Nitrogen Bond Rotation and Thermal Nitrogen Inversion in Heterocumulene OSNSO. Journal of the American Chemical Society 2018, 140 (4) , 1231-1234.
    9. Luke A. Farmer, Evan A. Haidasz, Markus Griesser, and Derek A. Pratt . Phenoxazine: A Privileged Scaffold for Radical-Trapping Antioxidants. The Journal of Organic Chemistry 2017, 82 (19) , 10523-10536.
    10. Jean-Philippe R. Chauvin, Markus Griesser, and Derek A. Pratt . Hydropersulfides: H-Atom Transfer Agents Par Excellence. Journal of the American Chemical Society 2017, 139 (18) , 6484-6493.
    11. Zosia A. M. Zielinski and Derek A. Pratt . Lipid Peroxidation: Kinetics, Mechanisms, and Products. The Journal of Organic Chemistry 2017, 82 (6) , 2817-2825.
    12. Hans J. Reich and Robert J. Hondal . Why Nature Chose Selenium. ACS Chemical Biology 2016, 11 (4) , 821-841.
    13. Mario C. Foti . Use and Abuse of the DPPH• Radical. Journal of Agricultural and Food Chemistry 2015, 63 (40) , 8765-8776.
    14. Keith U. Ingold and Derek A. Pratt . Advances in Radical-Trapping Antioxidant Chemistry in the 21st Century: A Kinetics and Mechanisms Perspective. Chemical Reviews 2014, 114 (18) , 9022-9046.
    15. Carlos Bravo-Díaz. Advances in the control of lipid peroxidation in oil-in-water emulsions: kinetic approaches †. Critical Reviews in Food Science and Nutrition 2023, 63 (23) , 6252-6284.
    16. Luca Valgimigli. Lipid Peroxidation and Antioxidant Protection. Biomolecules 2023, 13 (9) , 1291.
    17. Tamara Martínez-Senra, Sonia Losada-Barreiro, Jose M. Hermida-Ramón, Ana M. Graña, Carlos Bravo-Díaz. Molecular Design of Interfaces of Model Food Nanoemulsions: A Combined Experimental and Theoretical Approach. Antioxidants 2023, 12 (2) , 484.
    18. Riccardo Matera, Elena Lucchi, Luca Valgimigli. Plant Essential Oils as Healthy Functional Ingredients of Nutraceuticals and Diet Supplements: A Review. Molecules 2023, 28 (2) , 901.
    19. Adam B. Riddell, Matthew R. A. Smith, Adrian L. Schwan. The generation and reactions of sulfenate anions. An update. Journal of Sulfur Chemistry 2022, 43 (5) , 540-592.
    20. Bifeng Zhu, Junjie Jiang, Bo Lu, Xiaolong Li, Xiaoqing Zeng. Fluoromethylsulfinyl radicals: spectroscopic characterization and photoisomerization via intramolecular hydrogen shift. Physical Chemistry Chemical Physics 2022, 24 (15) , 8881-8889.
    21. Ryosuke Masuda, Kei Goto. Modeling of selenocysteine-derived reactive intermediates utilizing a nano-sized molecular cavity as a protective cradle. 2022, 331-361.
    22. Konrad Skotnicki, Ireneusz Janik, Klaudia Sadowska, Grazyna Leszczynska, Krzysztof Bobrowski. Radiation-Induced Oxidation Reactions of 2-Selenouracil in Aqueous Solutions: Comparison with Sulfur Analog of Uracil. Molecules 2022, 27 (1) , 133.
    23. Marlene Costa, Josefa Freiría-Gándara, Sonia Losada-Barreiro, Fátima Paiva-Martins, Carolina Aliaga, Carlos Bravo-Díaz. Interfacial kinetics in olive oil-in-water nanoemulsions: Relationships between rates of initiation of lipid peroxidation, induction times and effective interfacial antioxidant concentrations. Journal of Colloid and Interface Science 2021, 604 , 248-259.
    24. Aditya Upadhyay, Raushan Kumar Jha, Monojit Batabyal, Tanoy Dutta, Apurba Lal Koner, Sangit Kumar. Janus -faced oxidant and antioxidant profiles of organo diselenides. Dalton Transactions 2021, 50 (41) , 14576-14594.
    25. Zhuang Wu, Lina Wang, Bo Lu, André K. Eckhardt, Peter R. Schreiner, Xiaoqing Zeng. Spectroscopic characterization and photochemistry of the vinylsulfinyl radical. Physical Chemistry Chemical Physics 2021, 23 (30) , 16307-16315.
    26. Marlene Costa, Sonia Losada-Barreiro, Fátima Paiva-Martins, Carlos Bravo-Díaz. Polyphenolic Antioxidants in Lipid Emulsions: Partitioning Effects and Interfacial Phenomena. Foods 2021, 10 (3) , 539.
    27. Prasad P. Phadnis. Synthesis Strategies for Organoselenium Compounds and Their Potential Applications in Human Life. 2021, 537-641.
    28. Mariluz Soula, Ross A. Weber, Omkar Zilka, Hanan Alwaseem, Konnor La, Frederick Yen, Henrik Molina, Javier Garcia-Bermudez, Derek A. Pratt, Kıvanç Birsoy. Metabolic determinants of cancer cell sensitivity to canonical ferroptosis inducers. Nature Chemical Biology 2020, 16 (12) , 1351-1360.
    29. Riccardo Amorati, Andrea Baschieri, Luca Valgimigli. The role of sulfur and heavier chalcogens in the chemistry of antioxidants. Phosphorus, Sulfur, and Silicon and the Related Elements 2019, 194 (7) , 638-642.
    30. Shohei Sase, Ryutaro Kimura, Ryosuke Masuda, Kei Goto. Model study on trapping of protein selenenic acids by utilizing a stable synthetic congener. New Journal of Chemistry 2019, 43 (18) , 6830-6833.
    31. Gemma M. Locke, Stefan S. R. Bernhard, Mathias O. Senge. Nonconjugated Hydrocarbons as Rigid‐Linear Motifs: Isosteres for Material Sciences and Bioorganic and Medicinal Chemistry. Chemistry – A European Journal 2019, 25 (18) , 4590-4647.
    32. Xuelin Dong, Guohai Deng, Zhuang Wu, Jian Xu, Bo Lu, Tarek Trabelsi, Joseph S. Francisco, Xiaoqing Zeng. Spectroscopic Identification of H 2 NSO and syn ‐ and anti ‐HNSOH Radicals. Angewandte Chemie 2018, 130 (25) , 7635-7639.
    33. Xuelin Dong, Guohai Deng, Zhuang Wu, Jian Xu, Bo Lu, Tarek Trabelsi, Joseph S. Francisco, Xiaoqing Zeng. Spectroscopic Identification of H 2 NSO and syn ‐ and anti ‐HNSOH Radicals. Angewandte Chemie International Edition 2018, 57 (25) , 7513-7517.
    34. Zhuang Wu, Jian Xu, Guohai Deng, Xianxu Chu, Liubov Sokolenko, Tarek Trabelsi, Joseph S. Francisco, André K. Eckhardt, Peter R. Schreiner, Xiaoqing Zeng. The Trifluoromethyl Sulfinyl and Oxathiyl Radicals. Chemistry – A European Journal 2018, 24 (7) , 1505-1508.
    35. Kareem A. Harrison, Evan A. Haidasz, Markus Griesser, Derek A. Pratt. Inhibition of hydrocarbon autoxidation by nitroxide-catalyzed cross-dismutation of hydroperoxyl and alkylperoxyl radicals. Chemical Science 2018, 9 (28) , 6068-6079.
    36. Markus Griesser, Jean-Philippe R. Chauvin, Derek A. Pratt. The hydrogen atom transfer reactivity of sulfinic acids. Chemical Science 2018, 9 (36) , 7218-7229.
    37. Riccardo Amorati, Andrea Baschieri, Adam Cowden, Luca Valgimigli. The Antioxidant Activity of Quercetin in Water Solution. Biomimetics 2017, 2 (4) , 9.
    38. Andrea Baschieri, Majlinda Daci Ajvazi, Judith Laure Folifack Tonfack, Luca Valgimigli, Riccardo Amorati. Explaining the antioxidant activity of some common non-phenolic components of essential oils. Food Chemistry 2017, 232 , 656-663.
    39. Jean‐Philippe R. Chauvin, Derek A. Pratt. On the Reactions of Thiols, Sulfenic Acids, and Sulfinic Acids with Hydrogen Peroxide. Angewandte Chemie 2017, 129 (22) , 6351-6355.
    40. Jean‐Philippe R. Chauvin, Derek A. Pratt. On the Reactions of Thiols, Sulfenic Acids, and Sulfinic Acids with Hydrogen Peroxide. Angewandte Chemie International Edition 2017, 56 (22) , 6255-6259.
    41. Riccardo Amorati, Luca Valgimigli, Caterina Viglianisi, Max Schmallegger, Dmytro Neshchadin, Georg Gescheidt. Proton‐Coupled Electron Transfer from Hydrogen‐Bonded Phenols to Benzophenone Triplets. Chemistry – A European Journal 2017, 23 (22) , 5299-5306.
    42. Riccardo Amorati, Andrea Baschieri, Gloria Morroni, Rossana Gambino, Luca Valgimigli. Peroxyl Radical Reactions in Water Solution: A Gym for Proton‐Coupled Electron‐Transfer Theories. Chemistry – A European Journal 2016, 22 (23) , 7924-7934.
    43. Jean-Philippe R. Chauvin, Evan A. Haidasz, Markus Griesser, Derek A. Pratt. Polysulfide-1-oxides react with peroxyl radicals as quickly as hindered phenolic antioxidants and do so by a surprising concerted homolytic substitution. Chemical Science 2016, 7 (10) , 6347-6356.
    44. Jean-Philippe R. Chauvin, Zosia A.M. Zielinski, Derek A. Pratt. Inspired by garlic: insights on the chemistry of sulfenic acids and the radical-trapping antioxidant activity of organosulfur compounds. Canadian Journal of Chemistry 2016, 94 (1) , 1-8.
    45. L. Carroll, M. J. Davies, D. I. Pattison. Reaction of low-molecular-mass organoselenium compounds (and their sulphur analogues) with inflammation-associated oxidants. Free Radical Research 2015, 49 (6) , 750-767.
    46. Bo Li, Feng Zheng, Jean-Philippe R. Chauvin, Derek A. Pratt. The medicinal thiosulfinates from garlic and Petiveria are not radical-trapping antioxidants in liposomes and cells, but lipophilic analogs are. Chemical Science 2015, 6 (11) , 6165-6178.
    47. Fei Li, Jun Liu, Sharon Rozovsky. RETRACTED: Glutathione peroxidase׳s reaction intermediate selenenic acid is stabilized by the protein microenvironment. Free Radical Biology and Medicine 2014, 76 , 127-135.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Your Mendeley pairing has expired. Please reconnect