Applications of Frontier Molecular Orbital Theory to Pericyclic Reactions

Houk, K. N.

doi:10.1016/b978-0-12-470502-9.50010-9

Cited by 67 publications

(4 citation statements)

References 160 publications

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“…Some cycloadditions seem to follow a stepwise, biradical mechanism, [1,2], a mechanism which might be available to reaction (l), but with a higher barrier (and larger A-factor) than the concerted process. Some recent calculations have uncovered multiple nonsynchronous transition states in the concerted formation of cyclohexene, [3,32], transition states which have significantly different barriers.…”

Section: Discussionmentioning

confidence: 99%

Rate of the retro‐Diels‐Alder dissociation of 1,2,3,6‐tetrahydropyridine over a wide temperature range

Sidhu

Kiefer

Lifshitz

et al. 1991

Int J of Chemical Kinetics

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Rate constants for the retro-Diels-Alder dissociation of 1,2,3,6-tetrahydropyridine, to 1,3-butadiene and methanimine, have been measured over 650-1450 K. To cover this range, three separate techniques were used at three laboratories: laser schlieren and single pulse shock tube methods, and a comparative rate flow system technique. The derived rate constants are extrapolated to the high-pressure limit with an RRKM model parameterized to fit the falloff observed in the laser-schlieren measurements. The resulting high-pressure rate constants show a reduction in activation energy of about 10 kcal/mol, comparing the isoelectronic cyclohexene, but little change in A-factor. There is an apparent increase in activation energy of 4 kcal/mol over the temperature range of these experiments, which is just outside probable error. Such a rise in activation energy is in marked contrast to the drop usually seen in simple bond fission, and may reflect a change from a concerted to a stepwise, biradical mechanism at high temperatures.

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Section: Discussionmentioning

confidence: 99%

Rate of the retro‐Diels‐Alder dissociation of 1,2,3,6‐tetrahydropyridine over a wide temperature range

Sidhu

Kiefer

Lifshitz

et al. 1991

Int J of Chemical Kinetics

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“…Figure c,d present the HOMO and the LUMO of RhB. Based on the Frontier orbital theory, HOMO and LUMO can determine the capacity of RhB molecule for accepting, losing, and transferring electrons. , Generally, the sites prone to losing electrons are likely to be attacked by electrophilic radicals, while the sites prone to accepting electrons are likely to be attacked by nucleophilic radicals . In addition, f is a numerical representation of this trend to be attacked by radicals.…”

Section: Resultsmentioning

confidence: 99%

Constructing a Z-Scheme Co₃O₄/BiOBr Heterojunction to Enhance Photocatalytic Peroxydisulfate Oxidation of High-Concentration Rhodamine B: Mechanism, Degradation Pathways, and Toxicological Evaluations

Zhang,

Xu,

et al. 2024

Inorg. Chem.

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Photocatalytic coupling technologies have emerged as popular strategies to increase the treatment efficiency of dyecontaining wastewater. Herein, the Z-scheme Co 3 O 4 /BiOBr heterojunction (Z-CBH) was constructed and developed as a photocatalytic peroxydisulfate (PDS) activator for the degradation of high-concentration Rhodamine B (RhB). Multiple testing techniques were employed to confirm the formation of Z-CBHs. When 0.1 g•L −1 of Z-CBH20 and 1.0 mmol•L −1 of PDS were added simultaneously under simulated sunlight irradiation, the RhB degradation efficiency could approach 91.3%. Its reaction rate constant (0.01231 min −1 ) was much beyond the sum of those in the Z-CBH20/light system (0.00436 min −1 ) and the PDS/light system (0.0062 min −1 ). h + , • OH, • O 2 − , SO 4•− , and 1 O 2 were detected as the dominant reactive species for RhB degradation. The potential mechanism of photocatalytic PDS oxidation was proposed. The possible intermediates were determined by highperformance liquid chromatography-quadrupole time-of-flight mass spectrometry assisted with density functional theory and Fukui theory. The possible degradation pathways of RhB degradation were put forward. The toxicological properties of RhB and its intermediates were evaluated by quantitative structure−activity relationship prediction. This work will not only provide a reference for developing photocatalytic persulfate activators but also gain an insight into the degradation pathways of RhB and the toxicity of its intermediates.

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“…Thus, the uneven shifting of the HOMO and LUMO levels resulted in the tuning of E g which depends on the following two factors: (a) frontier orbital interaction (FOI), and (b) charge transfer. According to frontier molecular orbital (FMO) theory, 59,60 interaction between frontier orbitals (HOMO and LUMO) leads to hybridization and reduces the energy gap between them. However, charge transfer from the QD moiety to the attached functional group leads to a reduction in the screening of electrons.…”

Section: B Electronic Propertiesmentioning

confidence: 99%

Tuning the electronic and optical properties of hg-C₃N₄ quantum dots with edge-functionalization: a computational perspective

Dange,

Roondhe,

Shukla

2024

J. Mater. Chem. C

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Applications of Frontier Molecular Orbital Theory to Pericyclic Reactions

Cited by 67 publications

References 160 publications

Rate of the retro‐Diels‐Alder dissociation of 1,2,3,6‐tetrahydropyridine over a wide temperature range

Rate of the retro‐Diels‐Alder dissociation of 1,2,3,6‐tetrahydropyridine over a wide temperature range

Constructing a Z-Scheme Co₃O₄/BiOBr Heterojunction to Enhance Photocatalytic Peroxydisulfate Oxidation of High-Concentration Rhodamine B: Mechanism, Degradation Pathways, and Toxicological Evaluations

Tuning the electronic and optical properties of hg-C₃N₄ quantum dots with edge-functionalization: a computational perspective

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Applications of Frontier Molecular Orbital Theory to Pericyclic Reactions

Cited by 67 publications

References 160 publications

Rate of the retro‐Diels‐Alder dissociation of 1,2,3,6‐tetrahydropyridine over a wide temperature range

Rate of the retro‐Diels‐Alder dissociation of 1,2,3,6‐tetrahydropyridine over a wide temperature range

Constructing a Z-Scheme Co3O4/BiOBr Heterojunction to Enhance Photocatalytic Peroxydisulfate Oxidation of High-Concentration Rhodamine B: Mechanism, Degradation Pathways, and Toxicological Evaluations

Tuning the electronic and optical properties of hg-C3N4 quantum dots with edge-functionalization: a computational perspective

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Constructing a Z-Scheme Co₃O₄/BiOBr Heterojunction to Enhance Photocatalytic Peroxydisulfate Oxidation of High-Concentration Rhodamine B: Mechanism, Degradation Pathways, and Toxicological Evaluations

Tuning the electronic and optical properties of hg-C₃N₄ quantum dots with edge-functionalization: a computational perspective