Molecular Structures of the Metastable Charge-Transfer Complexes of Benzene (and Toluene) With Bromine as the Pre-Reactive Intermediates in Electrophilic Aromatic Bromination

Authors

Alexandr V. Vasilyev, University of Houston
Sergey V. Lindeman, Marquette UniversityFollow
Jay K. Kochi, University of Houston

Document Type

Article

Language

eng

Publication Date

1-2002

Publisher

Royal Society of Chemistry

Source Publication

New Journal of Chemistry

Source ISSN

1144-0546

Abstract

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.

Comments

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.

Recommended Citation

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.
https://epublications.marquette.edu/chem_fac/674