Molecular Structures of the Metastable Charge-Transfer Complexes of Benzene (and Toluene) With Bromine as the Pre-Reactive Intermediates in Electrophilic Aromatic Bromination
Royal Society of Chemistry
New Journal of Chemistry
Successful crystallization and X-ray crystallographic analyses of the highly metastable (1∶1) complexes of bromine with benzene and toluene establish the unique (localized) structure B that differs in notable ways from the long-accepted (delocalized) structure A. Furthermore, we demonstrate the (highly structured) charge-transfer complexes [C6H6,Br2] and [CH3C6H5,Br2] to be the pre-reactive intermediates that are converted (via an overall Br+ transfer) to the Wheland intermediates in electrophilic aromatic bromination. The role of the dative ion pairs [C6H6˙+ Br2˙−] and [CH3C6H5˙+ Br2˙−] in the rate-limiting activation processes is underscored.
Vasilyev, Alexandr V.; Lindeman, Sergey V.; and Kochi, Jay K., "Molecular Structures of the Metastable Charge-Transfer Complexes of Benzene (and Toluene) With Bromine as the Pre-Reactive Intermediates in Electrophilic Aromatic Bromination" (2002). Chemistry Faculty Research and Publications. 674.
Accepted version. New Journal of Chemistry, Vol. 26, No. 5 (2002): 582-592. DOI. © 2002 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique. Used with permission.
Sergey V. Lindeman was affiliated with the University of Houston at the time of publication.