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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. / Shernyukov, Andrey V.; Genaev, Alexander M.; Salnikov, George E. et al.

In: Organic and Biomolecular Chemistry, Vol. 17, No. 15, 21.04.2019, p. 3781-3789.

Research output: Contribution to journal › Article › peer-review

Harvard

Shernyukov, AV, Genaev, AM, Salnikov, GE, Shubin, VG & Rzepa, HS 2019, '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', Organic and Biomolecular Chemistry, vol. 17, no. 15, pp. 3781-3789. https://doi.org/10.1039/C9OB00607A

APA

Shernyukov, A. V., Genaev, A. M., Salnikov, G. E., Shubin, V. G., & Rzepa, H. S. (2019). 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. Organic and Biomolecular Chemistry, 17(15), 3781-3789. https://doi.org/10.1039/C9OB00607A

Vancouver

Shernyukov AV, Genaev AM, Salnikov GE, Shubin VG, Rzepa HS. 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. Organic and Biomolecular Chemistry. 2019 Apr 21;17(15):3781-3789. doi: 10.1039/C9OB00607A

Author

Shernyukov, Andrey V. ; Genaev, Alexander M. ; Salnikov, George E. et al. / 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. In: Organic and Biomolecular Chemistry. 2019 ; Vol. 17, No. 15. pp. 3781-3789.

BibTeX

@article{fd6ce71f18d44245b6b3e8384c6cff3f,
title = "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",
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 Br 2n−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. ",
keywords = "ACID SYSTEMS, SUBSTITUTIONS, DENSITY, CATIONS",
author = "Shernyukov, {Andrey V.} and Genaev, {Alexander M.} and Salnikov, {George E.} and Shubin, {Vyacheslav G.} and Rzepa, {Henry S.}",
year = "2019",
month = apr,
day = "21",
doi = "10.1039/C9OB00607A",
language = "English",
volume = "17",
pages = "3781--3789",
journal = "Organic and Biomolecular Chemistry",
issn = "1477-0520",
publisher = "Royal Society of Chemistry",
number = "15",

}

RIS

TY - JOUR

T1 - Elevated reaction order of 1,3,5-tri-tert-butylbenzene bromination as evidence of a clustered polybromide transition state

T2 - a combined kinetic and computational study

AU - Shernyukov, Andrey V.

AU - Genaev, Alexander M.

AU - Salnikov, George E.

AU - Shubin, Vyacheslav G.

AU - Rzepa, Henry S.

PY - 2019/4/21

Y1 - 2019/4/21

N2 - 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 Br 2n−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.

AB - 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 Br 2n−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.

KW - ACID SYSTEMS

KW - SUBSTITUTIONS

KW - DENSITY

KW - CATIONS

UR - http://www.scopus.com/inward/record.url?scp=85064129451&partnerID=8YFLogxK

U2 - 10.1039/C9OB00607A

DO - 10.1039/C9OB00607A

M3 - Article

AN - SCOPUS:85064129451

VL - 17

SP - 3781

EP - 3789

JO - Organic and Biomolecular Chemistry

JF - Organic and Biomolecular Chemistry

SN - 1477-0520

IS - 15

ER -

ID: 19355395