Probing Radical Pathways in Electrophilic Addition of Halogens: Classical vs. Bridged Intermediates

Authors

Lisa George, Marquette University
Aimable Kalume, Marquette UniversityFollow
Scott Reid, Marquette UniversityFollow

Document Type

Article

Publication Date

12-3-2012

Source Publication

Chemical Physics Letters

Source ISSN

0009-2614

Abstract

We examine radical mediated pathways in electrophilic addition to the simplest alkene, ethylene, where the structure of the radical intermediate has been extensively debated. Starting from the π-complex with a dihalogen, C₂H₄⋯I₂, isolated in an inert matrix, we initiate reaction by photolytically cleaving the I₂ bond. We succeed in trapping and spectroscopically interrogating the symmetrically bridged radical complex, which calculations confirm is the global minimum on the C₂H₅I Potential Energy Surface (PES). Consistent with the participation of a bridged intermediate, radical addition preferentially but not exclusively yields the anti-stereoisomer of the 1,2-diiodoethane product.

Comments

Accepted version. Chemical Physics Letters, Vol. 554, No. 3 (December 2012): 86–89. DOI. © 2012 Elsevier. Used with permission.

Recommended Citation

George, Lisa; Kalume, Aimable; and Reid, Scott, "Probing Radical Pathways in Electrophilic Addition of Halogens: Classical vs. Bridged Intermediates" (2012). Chemistry Faculty Research and Publications. 218.
https://epublications.marquette.edu/chem_fac/218