Styrene energetics and characterization of its conjugate base: An example of isotopic labeling gone awry

Alireza Fattahi; Lev Lis; Steven R. Kass

doi:10.1016/j.ijms.2016.03.009

Styrene energetics and characterization of its conjugate base: An example of isotopic labeling gone awry

Alireza Fattahi, Lev Lis, Steven R. Kass

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Abstract

The equilibrium acidity of styrene was measured (ΔH°_acid(PhCH[dbnd]CH₂) = 390.6 ± 0.5 kcal mol⁻¹) and its deprotonation site was revised from the ortho position on the aromatic ring to the α-hydrogen atom based upon deuterium-labeling studies and extensive computations. Somewhat surprisingly, the nature of the anionic base plays a critical role in properly determining the ionization site and avoiding misleading results due to extraordinary hydrogen–deuterium exchange. Bracketing the electron affinity of α-styryl radical (PhC[rad][dbnd]CH₂, 23.1 ± 3.4 kcal mol⁻¹) enabled the α-C[sbnd]H bond dissociation energy (100.1 ± 3.4 kcal mol⁻¹) of styrene and the effect of a phenyl substituent at an sp²-hybridized carbon to be determined. These results were compared to B3LYP, M06-2X, G3 and G4 computations.

Original language	English (US)
Pages (from-to)	163-167
Number of pages	5
Journal	International Journal of Mass Spectrometry
Volume	413
DOIs	https://doi.org/10.1016/j.ijms.2016.03.009
State	Published - Feb 1 2017

Bibliographical note

Funding Information:
Support from the National Science Foundation and the Minnesota Supercomputer Institute for Advanced Computational Research are gratefully acknowledged.

Publisher Copyright:
© 2016 Elsevier B.V.

Copyright:
Copyright 2017 Elsevier B.V., All rights reserved.

Keywords

Bond dissociation energy
Gas-phase energetics
Hydrogen–deuterium exchange
Styrene
α-Styryl radical

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10.1016/j.ijms.2016.03.009

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title = "Styrene energetics and characterization of its conjugate base: An example of isotopic labeling gone awry",

abstract = "The equilibrium acidity of styrene was measured (ΔH°acid(PhCH[dbnd]CH2) = 390.6 ± 0.5 kcal mol−1) and its deprotonation site was revised from the ortho position on the aromatic ring to the α-hydrogen atom based upon deuterium-labeling studies and extensive computations. Somewhat surprisingly, the nature of the anionic base plays a critical role in properly determining the ionization site and avoiding misleading results due to extraordinary hydrogen–deuterium exchange. Bracketing the electron affinity of α-styryl radical (PhC[rad][dbnd]CH2, 23.1 ± 3.4 kcal mol−1) enabled the α-C[sbnd]H bond dissociation energy (100.1 ± 3.4 kcal mol−1) of styrene and the effect of a phenyl substituent at an sp2-hybridized carbon to be determined. These results were compared to B3LYP, M06-2X, G3 and G4 computations.",

keywords = "Bond dissociation energy, Gas-phase energetics, Hydrogen–deuterium exchange, Styrene, α-Styryl radical",

author = "Alireza Fattahi and Lev Lis and Kass, {Steven R.}",

note = "Funding Information: Support from the National Science Foundation and the Minnesota Supercomputer Institute for Advanced Computational Research are gratefully acknowledged. Publisher Copyright: {\textcopyright} 2016 Elsevier B.V. Copyright: Copyright 2017 Elsevier B.V., All rights reserved.",

year = "2017",

month = feb,

day = "1",

doi = "10.1016/j.ijms.2016.03.009",

language = "English (US)",

volume = "413",

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T1 - Styrene energetics and characterization of its conjugate base

T2 - An example of isotopic labeling gone awry

AU - Fattahi, Alireza

AU - Lis, Lev

AU - Kass, Steven R.

N1 - Funding Information: Support from the National Science Foundation and the Minnesota Supercomputer Institute for Advanced Computational Research are gratefully acknowledged. Publisher Copyright: © 2016 Elsevier B.V. Copyright: Copyright 2017 Elsevier B.V., All rights reserved.

PY - 2017/2/1

Y1 - 2017/2/1

N2 - The equilibrium acidity of styrene was measured (ΔH°acid(PhCH[dbnd]CH2) = 390.6 ± 0.5 kcal mol−1) and its deprotonation site was revised from the ortho position on the aromatic ring to the α-hydrogen atom based upon deuterium-labeling studies and extensive computations. Somewhat surprisingly, the nature of the anionic base plays a critical role in properly determining the ionization site and avoiding misleading results due to extraordinary hydrogen–deuterium exchange. Bracketing the electron affinity of α-styryl radical (PhC[rad][dbnd]CH2, 23.1 ± 3.4 kcal mol−1) enabled the α-C[sbnd]H bond dissociation energy (100.1 ± 3.4 kcal mol−1) of styrene and the effect of a phenyl substituent at an sp2-hybridized carbon to be determined. These results were compared to B3LYP, M06-2X, G3 and G4 computations.

AB - The equilibrium acidity of styrene was measured (ΔH°acid(PhCH[dbnd]CH2) = 390.6 ± 0.5 kcal mol−1) and its deprotonation site was revised from the ortho position on the aromatic ring to the α-hydrogen atom based upon deuterium-labeling studies and extensive computations. Somewhat surprisingly, the nature of the anionic base plays a critical role in properly determining the ionization site and avoiding misleading results due to extraordinary hydrogen–deuterium exchange. Bracketing the electron affinity of α-styryl radical (PhC[rad][dbnd]CH2, 23.1 ± 3.4 kcal mol−1) enabled the α-C[sbnd]H bond dissociation energy (100.1 ± 3.4 kcal mol−1) of styrene and the effect of a phenyl substituent at an sp2-hybridized carbon to be determined. These results were compared to B3LYP, M06-2X, G3 and G4 computations.

KW - Bond dissociation energy

KW - Gas-phase energetics

KW - Hydrogen–deuterium exchange

KW - Styrene

KW - α-Styryl radical

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ER -

Styrene energetics and characterization of its conjugate base: An example of isotopic labeling gone awry

Abstract

Bibliographical note

Keywords

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