Symmetry-adapted reaction electronic flux in cycloaddition reactions

Villegas‐Escobar, Nery; Vogt-Geisse, Stefan; Gutiérrez‐Oliva, Soledad; Toro–Labbé, Alejandro

doi:10.1007/s00214-016-1933-6

Cited by 11 publications

(18 citation statements)

References 48 publications

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“…In this section the SA-REF profiles are discussed. The C s symmetry pathway in which the cycloaddition between C 60 and cyclopentadiene takes place allows the obtention of two SA-REFs: J A (ξ * ) and J A (ξ * ), following the irreducible representation of G. The J A (ξ * ) and J A (ξ * ) fluxes account for π and σ bonding information as previously reported [62]. The symmetrized orbital representation (A and A ) along with the wavefunction of the reaction under consideration is depicted in Figure 5.…”

Section: Symmetry-adapted Reaction Electronic Fluxmentioning

confidence: 83%

“…The main event here is the weakening of the π bonds centered in the C1-C1 bond in fullerene and the C α -C β and C α -C β bonds in cyclopentadiene (see Figure 1 for labeling of atoms). The weakening and subsequent breaking of these bonds is prompted by an strong Pauli electrostatic repulsion as the reactants approach one another [44,62]. At the J A (ξ * ) minimum denoted by (I), it is observed that the C α -C β and C α -C β bonds have only changed by 0.01Å .The C1-C1 bond remains unchanged with respect to the (RC) structure, which supports the idea that up to this point weakening over breaking processes are taking place.…”

Section: Symmetry-adapted Reaction Electronic Fluxmentioning

confidence: 99%

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Decomposition of the electronic activity in competing [5,6] and [6,6] cycloaddition reactions between C₆₀ and cyclopentadiene

Villegas‐Escobar

Poater

Solà

et al. 2019

Phys. Chem. Chem. Phys.

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Section: Symmetry-adapted Reaction Electronic Fluxmentioning

confidence: 83%

Section: Symmetry-adapted Reaction Electronic Fluxmentioning

confidence: 99%

Decomposition of the electronic activity in competing [5,6] and [6,6] cycloaddition reactions between C₆₀ and cyclopentadiene

Villegas‐Escobar

Poater

Solà

et al. 2019

Phys. Chem. Chem. Phys.

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“…The IRC results were used in a further stage where a more detailed analysis was performed through the reaction force (RF) formalism . It is important to point out that the RF concept can deal with unimolecular reactions in comparison with other related methods as the one based on a distortion‐interaction model …”

Section: Computational Methodlogymentioning

confidence: 99%

“…[17] It is important to point out that the RF concept can deal with unimolecular reactions in comparison with other related methods as the one based on a distortioninteraction model. [18][19][20][21] The reader is referred to the appropriate references [22][23][24] to review the original formulation of the RF concept. Here, it is directly indicated that, from the IRC results, the RF can be readily defined as follows:…”

Section: Computational Methodlogymentioning

confidence: 99%

Theoretical study of the furfuryl benzoate and furfuryl acetate pyrolysis

Mora

Rincón

Torres

et al. 2017

J of Physical Organic Chem

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In the present work, the pyrolysis reaction mechanism of both furfuryl benzoate and furfuryl acetate was evaluated at the M06/6‐311++g(d,p) level. The uncommon methylenecyclobutenone compound and either the benzoic or the acetic acid were determined as the products of a multistep process consisting in two [3 + 3] rearrangements and a subsequent hydrogen α‐elimination step, through a cyclic 5‐membered transition state (TS), being the latter the rate‐limiting step for both reactants. Furthermore, a deeper analysis on the basis of the reaction force formalism showed that the TS is formed in two stages: The first one is characterized by the weakening of the C─O bond, and the second one is where the H atom is transferred from the C atom to its nearest O atom. The H─O bond formation was determined to contribute the most to the electronic activity occurring during the TS formation as suggested by a reaction electronic flux analysis. Accordingly, natural bond orbital calculations showed that the most significant changes occur in the charge distribution of the O and H atoms. Finally, a negligible effect of the substituting group on the reaction was determined since similar activation energies were obtained for the pyrolysis of furfuryl benzoate and furfuryl acetate; however, a minor difference was evidenced in the reaction force results. In this sense, the structural contribution to the activation energy is larger than the electronic one for the furfuryl benzoate reaction, w1SR>w2SR, whereas the opposite is observed for the furfuryl acetate reaction, w1SR>w2SR.

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“…in different types of cycloadditions are analyzed by means of the reaction force constant 65,66 , reaction electronic flux 67 , and electronic stress 68 , which have been shown to be effective for this purpose. Very recently, Cremer et al 69 analyzed the reaction mechanism of the cycloaddition of ten 1,3-dipoles with two dipolarophiles (ethylene and acetylene) using the unified reaction valley approach.…”

Section: On the Reaction Mechanism Of 13-dipolar Cycloadditionsmentioning

confidence: 99%

On the outside looking in: rethinking the molecular mechanism of 1,3-dipolar cycloadditions from the perspective of bonding evolution theory. The reaction between cyclic nitrones and ethyl acrylate

Adjieufack

Ndassa

Patouossa

et al. 2017

Phys. Chem. Chem. Phys.

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In this work we report on the progress that has been made towards gaining an understanding of the molecular mechanism of 1,3-dipolar cycloadditions using the bonding evolution theory (BET). A detailed analysis of the flow of electron density along the reaction pathway of the formal 1,3-dipolar cycloaddition reaction between cyclic nitrones (pyrroline-1-oxide and 2,3,4,5 tetrahydropyridine-1-oxide) and ethyl acrylate, as a case study, allowed the nature of the molecular mechanisms to be characterized.The present study provides a deep insight into the reaction mechanism, based on the electron density rearrangements given by the structural stability domains, and their connection with the bond breaking/forming processes along the reaction pathway.Electron pushing formalism is a powerful tool to describe chemical reactivity. Here, we show how the Lewis structures can be recovered and how curly arrows describe electron density transfers in chemical reaction mechanisms based on the BET results. The reaction mechanism is described by four consecutive events taking place as the reaction progresses: 1) the population of the initial N−C double bond is transferred to the N and C atoms; 2) the population of the initial double C-C bond is transferred to the C atoms.Along the ortho pathway the next steps are: 3) the C−C bond-forming, and 4) the O-C 2 bond-forming process. The order of 3) and 4) is inverted in the meta channel. Based on the sequence of the structural stability domains along the intrinsic reaction coordinate, a new synchronicity index is proposed, allowing us to classify and quantify the (a)synchronicity of the 1,3-DC reactions and, therefore, the nature of the reaction mechanism.3

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Symmetry-adapted reaction electronic flux in cycloaddition reactions

Cited by 11 publications

References 48 publications

Decomposition of the electronic activity in competing [5,6] and [6,6] cycloaddition reactions between C₆₀ and cyclopentadiene

Decomposition of the electronic activity in competing [5,6] and [6,6] cycloaddition reactions between C₆₀ and cyclopentadiene

Theoretical study of the furfuryl benzoate and furfuryl acetate pyrolysis

On the outside looking in: rethinking the molecular mechanism of 1,3-dipolar cycloadditions from the perspective of bonding evolution theory. The reaction between cyclic nitrones and ethyl acrylate

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Symmetry-adapted reaction electronic flux in cycloaddition reactions

Cited by 11 publications

References 48 publications

Decomposition of the electronic activity in competing [5,6] and [6,6] cycloaddition reactions between C60 and cyclopentadiene

Decomposition of the electronic activity in competing [5,6] and [6,6] cycloaddition reactions between C60 and cyclopentadiene

Theoretical study of the furfuryl benzoate and furfuryl acetate pyrolysis

On the outside looking in: rethinking the molecular mechanism of 1,3-dipolar cycloadditions from the perspective of bonding evolution theory. The reaction between cyclic nitrones and ethyl acrylate

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Decomposition of the electronic activity in competing [5,6] and [6,6] cycloaddition reactions between C₆₀ and cyclopentadiene

Decomposition of the electronic activity in competing [5,6] and [6,6] cycloaddition reactions between C₆₀ and cyclopentadiene