Hydroxide Chemoselectivity Changes with Water MicrosolvationClick to copy article linkArticle link copied!
- Sapir Willdorf-CohenSapir Willdorf-CohenThe Wolfson Department of Chemical Engineering, Technion-Israel Institute of Technology, Haifa 3200003, IsraelMore by Sapir Willdorf-Cohen
- Alexander KaushanskyAlexander KaushanskySchulich Faculty of Chemistry, Technion-Israel Institute of Technology, Haifa 3200003, IsraelMore by Alexander Kaushansky
- Dario R. Dekel*Dario R. Dekel*Email: [email protected]The Wolfson Department of Chemical Engineering, Technion-Israel Institute of Technology, Haifa 3200003, IsraelThe Nancy & Stephen Grand Technion Energy Program (GTEP), Technion-Israel Institute of Technology, Haifa 3200003, IsraelMore by Dario R. Dekel
- Charles E. Diesendruck*Charles E. Diesendruck*Email: [email protected]Schulich Faculty of Chemistry, Technion-Israel Institute of Technology, Haifa 3200003, IsraelThe Nancy & Stephen Grand Technion Energy Program (GTEP), Technion-Israel Institute of Technology, Haifa 3200003, IsraelMore by Charles E. Diesendruck
Abstract

Solvent molecules are known to affect chemical reactions, especially if they interact with one or more of the reactants or catalysts. In ion microsolvation, i.e., solvent molecules in the first solvation sphere, strong electronic interactions are created, leading to significant changes in charge distribution and consequently on their nucleophilicity/electrophilicity and acidity/basicity. Despite a long history of research in the field, fundamental issues regarding the effects of ion microsolvation are still open, especially in the condensed phase. Using reactions between hydroxide and relatively stable quaternary ammonium salts as an example, we show that water microsolvation can change hydroxide’s chemoselectivity by differently affecting its basicity and nucleophilicity. In this example, the hydroxide reactivity as a nucleophile is less affected by water microsolvation than its reactivity as a base. These disparities are discussed by calculating and comparing oxidation potentials and polarizabilities of the different water–hydroxide clusters.
Cited By
Smart citations by scite.ai include citation statements extracted from the full text of the citing article. The number of the statements may be higher than the number of citations provided by ACS Publications if one paper cites another multiple times or lower if scite has not yet processed some of the citing articles.
This article is cited by 11 publications.
- Ritu Kumari, Vineeta Chaturvedi, Mudit Pithi, Avik K. Pati. Microsolvation-Driven Hours-Long Spectral Dynamics in Phenoxazine Dyes. The Journal of Physical Chemistry A 2025, 129
(1)
, 82-93. https://doi.org/10.1021/acs.jpca.4c06314
- Xiangyu Wu, Chongyang Zhao, Shaowen Zhang, Jing Xie. Shapeshifting Nucleophile Singly Hydrated Hydroperoxide Anion Leads to the Occurrence of the Thermodynamically Unfavored SN2 Product. The Journal of Physical Chemistry A 2024, 128
(12)
, 2393-2398. https://doi.org/10.1021/acs.jpca.4c01159
- Sapir Willdorf-Cohen, Avital Zhegur-Khais, Julia Ponce-González, Saja Bsoul-Haj, John R. Varcoe, Charles E. Diesendruck, Dario R. Dekel. Alkaline Stability of Anion-Exchange Membranes. ACS Applied Energy Materials 2023, 6
(2)
, 1085-1092. https://doi.org/10.1021/acsaem.2c03689
- Zhiwei Ren, Yun Zhao, Yangkai Han, Tao Wei, Jiaqi Sun, Zhilin Jiao, Xinyi Liu, Haitao Zhang, Zhigang Shao. Improving Alkali Stability of Anion Exchange Membrane by a Super Water‐Retention Strategy. Advanced Functional Materials 2025, 66 https://doi.org/10.1002/adfm.202423460
- Pegah Mansouri Bakvand, Dong Pan, Andrit Allushi, Patric Jannasch. Tuning the Performance of Poly(quaterphenyl piperidinium) Anion‐Exchange Membranes by Monomer Configuration. Advanced Energy Materials 2024, https://doi.org/10.1002/aenm.202402869
- Kanika Aggarwal, Songlin Li, Sally Nijem, Dario R. Dekel, Charles E. Diesendruck. Polymer Backbone Chemistry Shapes the Alkaline Stability of Metallopolymer Anion‐Exchange Membranes. Chemistry – A European Journal 2024, 30
(20)
https://doi.org/10.1002/chem.202400029
- Qianjun Ling, Chenxi Wang, Tao Wang, Shanzhong Yang, Xueliang Li, Haibing Wei, Yunsheng Ding. Beyond Small Molecular Cations: Elucidating the Alkaline Stability of Cationic Moieties at the Membrane Scale. ChemSusChem 2024, 17
(5)
https://doi.org/10.1002/cssc.202301656
- Qianjun Ling, Tao Wang, Tao Jiang, Yunsheng Ding, Haibing Wei. Molecular weight impacts the alkaline stability of poly(terphenylene alkylene) anion exchange membranes. Journal of Membrane Science 2024, 694 , 122407. https://doi.org/10.1016/j.memsci.2024.122407
- Wei Ting Gao, Xue Lang Gao, Yvonne Shuen Lann Choo, Jia Jun Wang, Zhi Hong Cai, Qiu Gen Zhang, Ai Mei Zhu, Qing Lin Liu. Durable dual-methylpiperidinium crosslinked poly(binaphthyl-co-terphenyl piperidinium) anion exchange membranes with high ion transport and electrochemical performance. Chemical Engineering Journal 2023, 466 , 143107. https://doi.org/10.1016/j.cej.2023.143107
- Ramesh K. Singh, John C. Douglin, Lanjie Jiang, Karam Yassin, Simon Brandon, Dario R. Dekel. CoOx-Fe3O4/N-rGO Oxygen Reduction Catalyst for Anion-Exchange Membrane Fuel Cells. Energies 2023, 16
(8)
, 3425. https://doi.org/10.3390/en16083425
- Pegah Mansouri Bakvand, Patric Jannasch. Poly(arylene alkylene)s with pendent benzyl-tethered ammonium cations for anion exchange membranes. Journal of Membrane Science 2023, 668 , 121229. https://doi.org/10.1016/j.memsci.2022.121229
Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.
Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.
The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.