Photochemical Dehalogenation of Aryl Halides: Importance of Halogen Bonding

Elhage, Ayda; Costa, Paolo; Nasim, Amrah; Lanterna, Anabel E.; Scaiano, Juan C.

Abstract

Upon UVA irradiation, aryl halides can undergo dehalogenation in the presence of bases and methanol as a hydrogen donor. This catalyst-free photochemical dehalogenation is furnished through a facile radical chain reaction under mild conditions. The chain reaction follows UVA irradiation of the reaction mixture in a transition-metal-free environment. Mechanistic studies support a chain mechanism in which initiation involves absorption by a methoxide-bromoarene complex facilitated by halogen-bonding interactions. The methoxide-bromine interaction leads to a weakened Br-C bond that is prone to facile cleavage during the initiation and propagation steps.

Citation

Elhage, A., Costa, P., Nasim, A., Lanterna, A. E., & Scaiano, J. C. (2019). Photochemical Dehalogenation of Aryl Halides: Importance of Halogen Bonding. Journal of Physical Chemistry A, 123(47), 10224-10229. https://doi.org/10.1021/acs.jpca.9b06716

• Journal Article Type: Article
• Acceptance Date: Oct 29, 2019
• Online Publication Date: Oct 29, 2019
• Publication Date: Nov 27, 2019
• Deposit Date: Jun 22, 2020
• Publicly Available Date: Oct 30, 2020
• Journal: The Journal of Physical Chemistry A
• Print ISSN: 1089-5639
• Electronic ISSN: 1520-5215
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 123
• Issue: 47
• Pages: 10224-10229
• DOI: https://doi.org/10.1021/acs.jpca.9b06716
• Keywords: Physical and Theoretical Chemistry
• Public URL: https://nottingham-repository.worktribe.com/output/4702084
• Publisher URL: https://pubs.acs.org/doi/abs/10.1021/acs.jpca.9b06716
• Additional Information: This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in The Journal of Physical Chemistry A, copyright © American Chemical Society after peer review. To access the final edited and published work see https://pubs.acs.org/doi/abs/10.1021/acs.jpca.9b06716.