Title

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

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

Chemical Physics Letters, Vol. 554, No. 3 (December 2012): 86–89. DOI.