Synlett 2015; 26(04): 471-478
DOI: 10.1055/s-0034-1379945
letter
© Georg Thieme Verlag Stuttgart · New York

Conditions and Edges for the Photochemical Generation of Short-Lived Aryl Cations: A Computational Approach

Carlotta Raviola
,
Davide Ravelli
,
Stefano Protti*
,
Angelo Albini
,
Maurizio Fagnoni
Further Information

Publication History

Received: 27 September 2014

Accepted after revision: 02 December 2014

Publication Date:
20 January 2015 (online)


Abstract

A DFT investigation on the conditions required for the photochemical generation of triplet aryl cations from differently para-substituted aryl halides has been carried out. The results showed a correlation between the energy change associated with the Ar–X bond heterolytic cleavage and the substituent Hammett–Brown constant (σp +). The method provides a means to predict the viability of the ArSN1 photosubstitution reaction.

Supporting Information

Primary Data