Elevated reaction order of 1,3,5-tri-tert-butylbenzene bromination as evidence of a clustered polybromide transition state: a combined kinetic and computational study

Literature Information

Publication Date 2019-03-20
DOI 10.1039/C9OB00607A
Impact Factor 3.876
Authors

Alexander M. Genaev, Vyacheslav G. Shubin, Henry S. Rzepa


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Abstract

The kinetics and mechanism of concurrent bromo-de-protonation and bromo-de-tert-butylation of 1,3,5-tri-tert-butylbenzene at different bromine concentrations were studied experimentally and theoretically. Both reactions have high order in bromine (experimental kinetic orders ∼5 and ∼7, respectively). According to quantum chemical DFT calculations, such high reaction orders are caused by participation of clustered polybromide anions Br2nāˆ’1– in transition states. Bromo-de-tert-butylation has a higher order due to its bigger reaction center demanding clusters of extended size. A significant primary deuterium kinetic isotope effect (KIE) for bromo-de-protonation is measured indicating proton removal is rate limiting, as confirmed by computed DFT models. The latter predict a larger value for the KIE than measured and possible explanations for this are discussed.

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Organic & Biomolecular Chemistry

Organic & Biomolecular Chemistry
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