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Theoretical Investigation into Rate-Determining Factors in Electrophilic Aromatic Halogenation
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Applied Physical Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Applied Physical Chemistry.ORCID iD: 0000-0003-3832-2331
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Applied Physical Chemistry.ORCID iD: 0000-0003-2673-075X
2018 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 122, no 12, p. 3270-3279Article in journal (Refereed) Published
Abstract [en]

The halogenation of monosubstituted benzenes in aqueous solvent was studied using density functional theory at the PCM-M06-2X/6-311G(d,p) level. The reaction with Cl-2 begins with the formation of C atom coordinated pi-complex and is followed by the formation of the sigma-complex, which is rate-determining. The final part proceeds via the abstraction of the proton by a water molecule or a weak base. We evaluated the use of the sigma-complex as a model for the rate-determining transition state (TS) and found that this model is more accurate the later the TS comes along the reaction coordinate. This explains the higher accuracy of the model for halogenations (late TS) compared to nitrations (early TS); that is, the more deactivated the substrate the later the TS. The halogenation with Br-2 proceeds with a similar mechanism as the corresponding chlorination, but the bromination has a very late rate-determining TS that is similar to the sigma-complex in energy. The iodination with ICl follows a different mechanism than chlorination and bromination. After the formation of the pi-complex, the reaction proceeds in a concerted manner without a sigma-complex. This reaction has a large primary hydrogen kinetic isotope effect in agreement with experimental observations.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2018. Vol. 122, no 12, p. 3270-3279
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-226789DOI: 10.1021/acs.jpca.7b10781ISI: 000429080300020PubMedID: 29505259Scopus ID: 2-s2.0-85044836973OAI: oai:DiVA.org:kth-226789DiVA, id: diva2:1203672
Note

QC 20180504

Available from: 2018-05-04 Created: 2018-05-04 Last updated: 2018-06-04Bibliographically approved

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Halldin Stenlid, JoakimBrinck, Tore

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