TY - JOUR

T1 - Molecular structures of the metastable charge-transfer complexes of benzene (and toluene) with bromine as the pre-reactive intermediates in electrophilic aromatic bromination

AU - Vasilyev, AV

AU - Lindeman, SV

AU - Kochi, JK

PY - 2002

Y1 - 2002

N2 - 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,Br-2] and [CH3C6H5,Br-2] 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.

AB - 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,Br-2] and [CH3C6H5,Br-2] 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.

KW - DONOR-ACCEPTOR COMPLEXES

KW - AB-INITIO

KW - CRYSTAL-STRUCTURES

KW - IODINE CHLORIDE

KW - PI-COMPLEXES

KW - SUBSTITUTION

KW - DYNAMICS

KW - HALOGENS

KW - STATE

KW - 1,1,1,3,3,3-HEXAFLUOROPROPAN-2-OL

U2 - 10.1039/b110169m

DO - 10.1039/b110169m

M3 - статья

VL - 26

SP - 582

EP - 592

JO - New Journal of Chemistry

JF - New Journal of Chemistry

SN - 1144-0546

IS - 5

ER -