Intriguing Chloride: Involvement of Chloride Ions in Proton Transfers
The proton transfer from carbon to a chloride ion and the proton transfer to a molecule of water promoted by chloride ions in the acid-catalyzed formation of hydroxamic acids from aldehydes and substituted nitrosobenzenes in mixed solvents have been proposed based on experimental and theoretical inv...
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| Format: | Article |
| Language: | English |
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MDPI AG
2022-02-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/27/4/1401 |
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| author | Viktor Pilepić Cvijeta Jakobušić Brala Stanko Uršić |
| author_facet | Viktor Pilepić Cvijeta Jakobušić Brala Stanko Uršić |
| author_sort | Viktor Pilepić |
| collection | DOAJ |
| description | The proton transfer from carbon to a chloride ion and the proton transfer to a molecule of water promoted by chloride ions in the acid-catalyzed formation of hydroxamic acids from aldehydes and substituted nitrosobenzenes in mixed solvents have been proposed based on experimental and theoretical investigations. The formation of uncommon contact ion pairs consisting of the nitrosocarbinolic cation intermediate and a chloride anion, followed by the proton transfer from a C-H moiety of the cation intermediate, has been proposed. The influence of chloride on the proton transfer to a water molecule of the solvent-separated nitrosocarbinolic-cation–chloride ion pair was investigated too. The insights are based on the obtained kinetic and other evidence with regard to (1) influences of chloride anions on the observed reaction rates and primary kinetic isotope effects (PKIE) in the reaction; (2) the observed variation of the PKIE-s and rates of the reaction when perchlorate anions are present along with the chloride ions; and (3) the consideration of a model of the nitrosocarbinolic-cation-intermediate—chloride ion pair and transition structure for the proposed proton transfers based on the ab initio calculations. |
| first_indexed | 2024-03-09T21:19:56Z |
| format | Article |
| id | doaj.art-8e7ab98b5f2348baba8f16fa8cfac574 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T21:19:56Z |
| publishDate | 2022-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-8e7ab98b5f2348baba8f16fa8cfac5742023-11-23T21:23:23ZengMDPI AGMolecules1420-30492022-02-01274140110.3390/molecules27041401Intriguing Chloride: Involvement of Chloride Ions in Proton TransfersViktor Pilepić0Cvijeta Jakobušić Brala1Stanko Uršić2Faculty of Pharmacy and Biochemistry, University of Zagreb, A. Kovačića 1, 10000 Zagreb, CroatiaFaculty of Pharmacy and Biochemistry, University of Zagreb, A. Kovačića 1, 10000 Zagreb, CroatiaFaculty of Pharmacy and Biochemistry, University of Zagreb, A. Kovačića 1, 10000 Zagreb, CroatiaThe proton transfer from carbon to a chloride ion and the proton transfer to a molecule of water promoted by chloride ions in the acid-catalyzed formation of hydroxamic acids from aldehydes and substituted nitrosobenzenes in mixed solvents have been proposed based on experimental and theoretical investigations. The formation of uncommon contact ion pairs consisting of the nitrosocarbinolic cation intermediate and a chloride anion, followed by the proton transfer from a C-H moiety of the cation intermediate, has been proposed. The influence of chloride on the proton transfer to a water molecule of the solvent-separated nitrosocarbinolic-cation–chloride ion pair was investigated too. The insights are based on the obtained kinetic and other evidence with regard to (1) influences of chloride anions on the observed reaction rates and primary kinetic isotope effects (PKIE) in the reaction; (2) the observed variation of the PKIE-s and rates of the reaction when perchlorate anions are present along with the chloride ions; and (3) the consideration of a model of the nitrosocarbinolic-cation-intermediate—chloride ion pair and transition structure for the proposed proton transfers based on the ab initio calculations.https://www.mdpi.com/1420-3049/27/4/1401chlorideproton transferkinetic isotope effectsion pair intermediates |
| spellingShingle | Viktor Pilepić Cvijeta Jakobušić Brala Stanko Uršić Intriguing Chloride: Involvement of Chloride Ions in Proton Transfers Molecules chloride proton transfer kinetic isotope effects ion pair intermediates |
| title | Intriguing Chloride: Involvement of Chloride Ions in Proton Transfers |
| title_full | Intriguing Chloride: Involvement of Chloride Ions in Proton Transfers |
| title_fullStr | Intriguing Chloride: Involvement of Chloride Ions in Proton Transfers |
| title_full_unstemmed | Intriguing Chloride: Involvement of Chloride Ions in Proton Transfers |
| title_short | Intriguing Chloride: Involvement of Chloride Ions in Proton Transfers |
| title_sort | intriguing chloride involvement of chloride ions in proton transfers |
| topic | chloride proton transfer kinetic isotope effects ion pair intermediates |
| url | https://www.mdpi.com/1420-3049/27/4/1401 |
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