Differences in reactivity between excited states of cis- and trans-1,3-pentadiene

Boué, Stéphane; Srinivasan, R.

doi:10.1021/ja00713a074

Cited by 35 publications

(5 citation statements)

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“…The conformations of 1,3‐butadiene have been a hot topic . Figure is the torsional potential energy curve (TPEC) of 1,3‐butadiene calculated with the six functionals, where the C 1 –C 2 double bond rotates around the C 2 –C 3 single bond for 360° in steps of 10°, and C 1 and C 2 are fixed on the same plane with hydrogen atoms bonded to them throughout the process.…”

Section: Resultsmentioning

confidence: 99%

A thorough understanding of the Diels–Alder reaction of 1,3‐butadiene and ethylene

Cui

Liu

2014

J of Physical Organic Chem

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The Diels-Alder (DA) reaction is one of the most important reactions in organic chemistry. The controversy surrounding this reaction as to whether it follows a concerted or stepwise mechanism has existed for a long time. The reaction of 1,3-butadiene and ethylene is the paradigmatic example of the DA reaction. We have reinvestigated the mechanism of this reaction using density functional theory. The theoretical study considered all types of possible pathways for the reaction of 1,3-butadiene and ethylene using six functionals at different rungs of Jacob's ladder. Therefore, a complete picture is given for a thorough understanding of the iconic DA reaction, and a new stationary point during the reaction processes has been reported for the first time. The calculated results indicated that three functionals, ωB97X-D, M06-2X, and B2-PLYP, of the fourth and fifth rungs of Jacob's ladder performed well in the investigation of the mechanism of this reaction and that the reliable basis set should be larger than 6-311+G(2d,p). The cis-1,3-butadiene more easily reacted with ethylene compared with 1,3-butadiene in the trans conformation. The concerted mechanism was found to be energetically favorable, whose energy barrier is around 10 kcal/mol lower than that of the stepwise mechanism. Two investigated solvents, toluene and CH 3 CN, had little impact on this simple DA reaction.

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Section: Resultsmentioning

confidence: 99%

A thorough understanding of the Diels–Alder reaction of 1,3‐butadiene and ethylene

Cui

Liu

2014

J of Physical Organic Chem

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“…3,[49][50][51] The barrier to rotation about the central bond is small and rotation to the less favorable, but reactive s-cis conformation is rapid. 3 Although the molar percentage for the s-gauche conformer is very small, the existence of the s-gauche conformer in the 1,3-butadiene sample makes it possible to induce the s-trans/s-gauche equilibrium ͓Eq.…”

Section: ͑2͒mentioning

confidence: 99%

Coexistence of 1,3-butadiene conformers in ionization energies and Dyson orbitals

Saha

Wang

Falzon

et al. 2005

The Journal of Chemical Physics

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The minimum-energy structures on the torsional potential-energy surface of 1,3-butadiene have been studied quantum mechanically using a range of models including ab initio Hartree-Fock and second-order Møller-Plesset theories, outer valence Green's function, and density-functional theory with a hybrid functional and statistical average orbital potential model in order to understand the binding-energy ͑ionization energy͒ spectra and orbital cross sections observed by experiments. The unique full geometry optimization process locates the s-trans-1,3-butadiene as the global minimum structure and the s-gauche-1,3-butadiene as the local minimum structure. The latter possesses the dihedral angle of the central carbon bond of 32.81°in agreement with the range of 30°-41°obtained by other theoretical models. Ionization energies in the outer valence space of the conformer pair have been obtained using Hartree-Fock, outer valence Green's function, and density-functional ͑statistical average orbital potentials͒ models, respectively. The Hartree-Fock results indicate that electron correlation ͑and orbital relaxation͒ effects become more significant towards the inner shell. The spectroscopic pole strengths calculated in the Green's function model are in the range of 0.85-0.91, suggesting that the independent particle picture is a good approximation in the present study. The binding energies from the density-functional ͑statisticaly averaged orbital potential͒ model are in good agreement with photoelectron spectroscopy, and the simulated Dyson orbitals in momentum space approximated by the density-functional orbitals using plane-wave impulse approximation agree well with those from experimental electron momentum spectroscopy. The coexistence of the conformer pair under the experimental conditions is supported by the approximated experimental binding-energy spectra due to the split conformer orbital energies, as well as the orbital momentum distributions of the mixed conformer pair observed in the orbital cross sections of electron momentum spectroscopy.

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“…The additional photoisomer could be the result of a photocyclization reaction. Indeed, the formation of cyclobutene and cyclopropene isomers has been shown to occur upon direct UV irradiation of 1,3-dienes. , Only one photoisomer was observed for ( Z )-1,1,2,3,4-PCBD, which was assigned to its E configuration.…”

Section: Resultsmentioning

confidence: 99%

Abatement of Polychoro-1,3-butadienes in Aqueous Solution by Ozone, UV Photolysis, and Advanced Oxidation Processes (O₃/H₂O₂ and UV/H₂O₂)

Lee

Merle

Rentsch

et al. 2016

Environ. Sci. Technol.

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The abatement of 9 polychloro-1,3-butadienes (CBDs) in aqueous solution by ozone, UV-C(254 nm) photolysis, and the corresponding advanced oxidation processes (AOPs) (i.e., O/HO and UV/HO) was investigated. The following parameters were determined for 9 CBDs: second-order rate constants for the reactions of CBDs with ozone (k) (<0.1-7.9 × 10 M s) or with hydroxyl radicals (k) (0.9 × 10 - 6.5 × 10 M s), photon fluence-based rate constants (k') (210-2730 m einstein), and quantum yields (Φ) (0.03-0.95 mol einstein). During ozonation of CBDs in a natural groundwater, appreciable abatements (>50% at specific ozone doses of 0.5 gO/gDOC to ∼100% at ≥1.0 gO/gDOC) were achieved for tetra-CBDs followed by (Z)-1,1,2,3,4-penta-CBD and hexa-CBD. This is consistent with the magnitude of the determined k and k. The formation of bromate, a potentially carcinogenic ozonation byproduct, could be significantly reduced by addition of HO. For a typical UV disinfection dose (400 J/m), various extents of phototransformations (10-90%) could be achieved. However, the efficient formation of photoisomers from CBDs with E/Z configuration must be taken into account because of their potential residual toxicity. Under UV-C(254 nm) photolysis conditions, no significant effect of HO addition on CBDs abatement was observed due to an efficient direct phototransformation of CBDs.

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Differences in reactivity between excited states of cis- and trans-1,3-pentadiene

Cited by 35 publications

References 2 publications

A thorough understanding of the Diels–Alder reaction of 1,3‐butadiene and ethylene

A thorough understanding of the Diels–Alder reaction of 1,3‐butadiene and ethylene

Coexistence of 1,3-butadiene conformers in ionization energies and Dyson orbitals

Abatement of Polychoro-1,3-butadienes in Aqueous Solution by Ozone, UV Photolysis, and Advanced Oxidation Processes (O₃/H₂O₂ and UV/H₂O₂)

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Differences in reactivity between excited states of cis- and trans-1,3-pentadiene

Cited by 35 publications

References 2 publications

A thorough understanding of the Diels–Alder reaction of 1,3‐butadiene and ethylene

A thorough understanding of the Diels–Alder reaction of 1,3‐butadiene and ethylene

Coexistence of 1,3-butadiene conformers in ionization energies and Dyson orbitals

Abatement of Polychoro-1,3-butadienes in Aqueous Solution by Ozone, UV Photolysis, and Advanced Oxidation Processes (O3/H2O2 and UV/H2O2)

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Abatement of Polychoro-1,3-butadienes in Aqueous Solution by Ozone, UV Photolysis, and Advanced Oxidation Processes (O₃/H₂O₂ and UV/H₂O₂)