Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 132, Issue 9, Pages 2907-2913Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja903856t
Keywords
-
Categories
Funding
- National Science Foundation [CHE-0548129, CHE-0547543, DGE-0333378]
- Cottrell Scholar of Research Corporation
Ask authors/readers for more resources
The hydroxyl radical (HO center dot) is a highly reactive oxygen-centered radical whose bimolecular rate constants for reaction with organic compounds (hydrogen atom abstraction) approach the diffusion-controlled limit in aqueous solution. The results reported herein show that hydroxyl radical is considerably less reactive in dipolar, aprotic solvents such as acetonitrile. This diminished reactivity is explained on the basis of a polarized transition state for hydrogen abstraction, in which the oxygen of the hydroxyl radical becomes highly negative and can serve as a hydrogen bond acceptor. Because acetonitrile cannot participate as a hydrogen bond donor, the transition state cannot be stabilized by hydrogen bonding, and the reaction rate is lower; the opposite is true when water is the solvent. This hypothesis explains hydroxyl radical reactivity both in solution and in the gas phase and may be the basis for a containment strategy used by Nature when hydroxyl radical is produced endogenously.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available