Singh, Ashi; Avinash, Kiran; Malaspina, Lorraine A; Banoo, Masoumeh; Alhameedi, Khidhir; Jayatilaka, Dylan; Grabowsky, Simon; Thomas, Sajesh Pynadath (2024). Dynamic Covalent Bonds in the Ebselen Class of Antioxidants Probed by X-ray Quantum Crystallography. Chemistry: a European journal, 30(14), e202303384. Wiley 10.1002/chem.202303384
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Chemistry_A_European_J_-_2023_-_Singh_-_Dynamic_Covalent_Bonds_in_the_Ebselen_Class_of_Antioxidants_Probed_by_X_ray_Quantum.pdf - Accepted Version Restricted to registered users only until 21 December 2024. Available under License Publisher holds Copyright. Download (1MB) | Request a copy |
Dynamic bonds are essential structural ingredients of dynamic covalent chemistry that involve reversible cleavage and formation of bonds. Herein, we explore the electronic characteristics of Se-N bonds in the organo-selenium antioxidant ebselen and its derivatives for their propensity to function as dynamic covalent bonds by employing high-resolution X-ray quantum crystallography and complementary computational studies. An analysis of the experimentally reconstructed X-ray wavefunctions reveals the salient electronic features of the Se-N bonds with very low electron density localized at the bonding region and a positive Laplacian value at the bond critical point. Bond orders and percentage covalency and ionicity estimated from the X-ray wavefunctions, along with localized orbital locator (LOL) and electron localization function (ELF) analyses show that the Se-N bond is unique in its closed shell-like features, despite being a covalent bond. Time-dependent DFT calculations simulate the cleavage of Se-N bonds in ebselen in the excited state, further substantiating their nature as dynamic bonds.
Item Type: |
Journal Article (Original Article) |
|---|---|
Division/Institute: |
08 Faculty of Science > Department of Chemistry, Biochemistry and Pharmaceutical Sciences (DCBP) |
UniBE Contributor: |
Malaspina, Lorraine, Grabowsky, Simon |
Subjects: |
500 Science > 570 Life sciences; biology 500 Science > 540 Chemistry |
ISSN: |
1521-3765 |
Publisher: |
Wiley |
Language: |
English |
Submitter: |
Pubmed Import |
Date Deposited: |
03 Jan 2024 16:31 |
Last Modified: |
10 Mar 2024 00:15 |
Publisher DOI: |
10.1002/chem.202303384 |
PubMed ID: |
38126954 |
Uncontrolled Keywords: |
Dynamic covalent bond Organic selenium Quantum crystallography X-ray wavefunction bonding analysis |
BORIS DOI: |
10.48350/190667 |
URI: |
https://boris.unibe.ch/id/eprint/190667 |
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