The Bell–Evans–Polanyi Principle and the regioselectivity of electrophilic aromatic substitution reactions

Wubbels, Gene G.

doi:10.1016/j.tetlet.2015.02.070

Cited by 10 publications

(6 citation statements)

References 16 publications

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“…From chemical principle, the relationship for intrinsic reaction barrier versus energy difference elaborated above leads us to mull the classical mechanistic approaches to access the kinetics–thermodynamics relationship of ESIPT, among which the Bell–Evans–Polanyi (BEP) principle, a long-standing semiempirical approach, ,− has received our attention. Considering ESIPT as a classical A–H bond breakage–reformation reaction, such as A–H + B → A + H–B, the BEP principle states that if the geometries and the curvature of PES at transition states are approximately the same along the reaction coordinate within a family of molecules, there is a linear relation between activation energy (Δ E a ) and Δ E T*–N* in the case of ESIPT, expressed as where the intercept Δ E 0 represents the referential activation energy for a family of derivatives when Δ E T*–N* = 0. α represents the character of the position of the transition state along the reaction coordinate, which should be in a range of 0 ≤ α ≤ 1 .…”

Section: Background and Introductionmentioning

confidence: 99%

Correlation between Kinetics and Thermodynamics for Excited-State Intramolecular Proton Transfer Reactions

2021

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Finding the relation between thermodynamics and kinetics for a reaction is of fundamental importance. Here, the thermodynamics and kinetics correlation of excited-state intramolecular proton transfer (ESIPT) was investigated by the TD-DFT calculation under the CAM-B3LYP/6-311+G** level. We choose the family 2-(2′-aminophyenyl)benzothiazole and its amino derivatives as paradigms, which all possess the NH-type intramolecular hydrogen bond (H-bond), and investigate the corresponding ESIPT reaction. The H-bond strength can be systematically tuned, so both activation energy ΔG ‡ and free energy difference between proton transfer tautomer (T*, product) and normal species (N*, reactant) ΔG T*–N* can be varied. To minimize the environmental interference such as solvent external H-bond and polarity perturbation, a nonpolar solvent such as cyclohexane is chosen as a bath with a polarizable continuum solvation model for the calculation. As a result, the comprehensive computational approach reveals a linear relationship between ΔG T*–N* and ΔG ‡, which can be expressed as ΔG ‡ = ΔG 0 + αΔG T*–N*. The fundamental insight is reminiscent of the Bell–Evans–Polanyi (BEP) principle where α represents the character of the position of the transition state along the proton motion coordinate. In other words, the more exergonic the ESIPT reaction is, the faster the proton transfer rate can be observed. To verify that such a correlation is not a sporadic event, another ESIPT family with an −OH proton, 1-hydroxy-11H-benzo[b]fluoren-11-one and its derivatives, was also investigated and proved to follow the BEP principle as well. Unlike the quantum mechanics description of proton transfer where either proton tunneling is dominant or solute/solvent is coupled in ESIPT, this work demonstrates that reaction kinetics and thermodynamics are strongly correlated within the same class of ESIPT molecules with an intrinsic barrier free from solvent perturbation, being faster with the more exergonic reaction.

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Section: Background and Introductionmentioning

confidence: 99%

Correlation between Kinetics and Thermodynamics for Excited-State Intramolecular Proton Transfer Reactions

2021

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“…These lead to the conclusion that a decrease in the reaction barrier should increase the reaction exothermicity. While the B‐E‐P principle has been applied to a number of reactions involving bond rearrangement, [9–14] the fundamental issue of whether the reaction parameters, e.g., transition‐state structure and reactive frequency, meet the criteria is often overlooked.…”

Section: Introductionmentioning

confidence: 99%

“…where E 0 is the intercept, and a is avalue characteristic of the transition state along the reaction coordinate,w hich should be in the range of 0 a < 1. These lead to the conclusion that adecrease in the reaction barrier should increase the reaction exothermicity.While the B-E-P principle has been applied to anumber of reactions involving bond rearrangement, [9][10][11][12][13][14] the fundamental issue of whether the reaction parameters,e .g., transition-state structure and reactive frequency, meet the criteria is often overlooked. In yet another instance,u pon excitation, changes in the electron density distribution are induced, where structure relaxation becomes au biquitous phenomenon.…”

Section: Introductionmentioning

confidence: 99%

Broadening the Horizon of the Bell–Evans–Polanyi Principle towards Optically Triggered Structure Planarization

et al. 2021

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Finding a relationship between kinetics and thermodynamics may be difficult. However, semi‐empirical rules exist to compensate for this shortcoming, among which the Bell–Evans–Polanyi (B‐E‐P) principle is an example for reactions involving bond breakage and reformation. We expand the B‐E‐P principle to a new territory by probing photoinduced structure planarization (PISP) of a series of dibenz[b,f]azepine derivatives incorporating bent‐to‐planar and rotation motion. The latter involves twisting of the partial double bond character, thereby inducing a barrier that is substituent dependent at the para N‐phenyl position. The transition‐state structure and frequency data satisfy and broaden the B‐E‐P principle to PISP reactions without bond rearrangement. Together with dual emissions during PISP, this makes possible harnessing of the kinetics/thermodynamics relationship and hence ratiometric luminescence properties for excited‐state structural transformations.

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“…This putative correlation permits one to avoid laborious and computationally expensive TS searches and still predict reactivity. ,,, In some cases, “product stability” played a role of one “descriptor” among others, which served as input parameters in a reactivity prediction model . The BEP principle has been used in a number of studies dedicated to diverse types of reactions, where the correlations were reasonable. − For some other reactions the correlations were reported to be poor, nonexistent, or otherwise not completely satisfactory. − We must point out that in some cases few data points, , as few as three, were used to draw conclusions about the validity of the correlation.…”

Section: Intrinsic Reactivity Of Aromatic Ringsmentioning

confidence: 99%

Large Computational Survey of Intrinsic Reactivity of Aromatic Carbon Atoms with Respect to a Model Aldehyde Oxidase

Levine,

Jacobson,

Bochevarov

2023

J. Chem. Theory Comput.

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The Bell–Evans–Polanyi Principle and the regioselectivity of electrophilic aromatic substitution reactions

Cited by 10 publications

References 16 publications

Correlation between Kinetics and Thermodynamics for Excited-State Intramolecular Proton Transfer Reactions

Correlation between Kinetics and Thermodynamics for Excited-State Intramolecular Proton Transfer Reactions

Broadening the Horizon of the Bell–Evans–Polanyi Principle towards Optically Triggered Structure Planarization

Large Computational Survey of Intrinsic Reactivity of Aromatic Carbon Atoms with Respect to a Model Aldehyde Oxidase

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