Topological unraveling of the [3+2] cycloaddition (32CA) reaction between <i>N</i>-methylphenylnitrone and styrene catalyzed by the chromium tricarbonyl complex using electron localization function and catastrophe theory

Adjieufack, Abel Idrice; Ongagna, Jean Moto; Tchidjo, Joseline Flore Kenmogne; Ndassa, Ibrahim Mbouombouo

doi:10.1039/d1nj04121e

Cited by 7 publications

(2 citation statements)

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“…To perform these analyses quantitatively, Krokidis and Silvi proposed the joint use of ELF topology [11] and Thom's catastrophe theory (CT) [14] within the Bonding Evolution Theory, BET [15,16] as a new tool for studying the electronic changes occurring along a given chemical rearrangement. BET has been used as an appropriate quantum tool to gain a deep insight into the molecular mechanisms on a wide range of chemical reactions including denitrogenations, decompositions, formation of anionic complexes, cycloadditions [17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] and even radical reactions [33].…”

Section: Introductionmentioning

confidence: 99%

Deciphering the Molecular Mechanism of Intramolecular Reactions from the Perspective of Bonding Evolution Theory

et al. 2022

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The molecular mechanisms of three intramolecular rearrangements (I, the rearrangement of allyloxycycloheptatriene to yield tricyclic ketones; II, the cycloaddition of a nitrone-alkene to render two tricyclic isoxazolidines; and III, the decomposition of N-carbamoyl-L-proline in tetrahydro-1H-pyrrolo[1,2-c]imidazole-1,3(2H)-dione plus water, or tetrahydro-1H,3H-pyrrolo[1,2-c]oxazole-1,3-dione plus ammonia) have been studied by means of the bonding evolution theory (BET). The thermal rearrangement I is composed by a sigmatropic rearrangement coupled to an intramolecular Diels–Alder reaction. The sigmatropic reaction comprises four steps: (1) rupture of an O-C single chemical bond, (2) transformation of a C-O single to double bond, (3) creation of pseudo-radical centers on carbon atoms coupled with a double C-C bond evolving to single and the other C-C double bond migration, and (4) formation of the new C-C single bond. For the Diels–Alder reaction, the process can be described as an initial formation of up to four monosynaptic V(C) basins in two successive steps, coupled with the loss of the double bond character of the three initial double bonds, followed by the consecutive formation of two new C-C bonds, with the new double C-C bond formation sensed in between the formation of the first and the second C-C bonds. For reaction II, the bond forming process is described by the depopulation of N-C and C-C double bonds with the creation of a V(N) and two V(C) monosynaptic basins, followed by an O-C and C-C bond-forming processes via the creation of V(O,C) and V(C,C) disynaptic basins. Finally, for the thermal decomposition III, the reaction mechanism for the water elimination takes place in four events which can be summarized as follows: (1) the depopulation of V(N) with the formation of C-N, (2) the rupture of the C-O bond with transfer of its population to V(O), (3) the restoration of an N nitrogen lone pair via H-N bond cleavage, and (4) the formation of O-H illustrating the water molecule release. For the case of deamination, the events (1) and (2) correspond to the breaking and forming process of H-O and H-N bonds, respectively, while last events deal with the C-O bond formation and the elimination of the NH3 molecule.

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Section: Introductionmentioning

confidence: 99%

Deciphering the Molecular Mechanism of Intramolecular Reactions from the Perspective of Bonding Evolution Theory

et al. 2022

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“…They are also involved in several synthesis mechanisms of natural compounds and physiologically active heterocyclic molecules. − Heterocycles constitute a basic skeleton for some wide chemical compounds having biological, pharmacological, and industrial interests. Hence, heterocyclic chemistry has become the focus of a large community of experimental and theoretical chemists. − …”

Section: Introductionmentioning

confidence: 99%

How a Chromium Tricarbonyl Complex Catalyzes the [3 + 2] Cycloaddition Reaction of N-Substituted Phenylnitrones with Styrene: A Molecular Electron Density Theory Analysis

et al. 2022

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The reaction mechanisms of [3 + 2] cycloaddition (32CA) between two N-substituted phenylnitrones (NPPN and NtBPN) and styrene (STY) in the presence of a chromium tricarbonyl complex (Cr(CO)3) have been studied within the framework of molecular electron density theory at the MPWB1K/6-311G(d,p) level. Activation energy analysis reveals that these 32CA reactions take place with high activation barriers due to their non-polar character and with the exo/ortho approach as a favorable reaction path. The activation energy of TS1 series (NPPN) is about 5–6 kcal/mol lower than that of the TS2 series (NtBPN), due to the steric hindrance of tert-butyl at the TS2 structures. Coordination of chromium tricarbonyl to each reactant to form the corresponding complex slightly increases the nucleophilic and electrophilic character of NPPN:Cr, NtBPN:Cr, and STY:Cr, which can be considered a strong nucleophile and electrophile able to participate in a polar 32CA reaction. This polar character in the presence of the chromium tricarbonyl complex was verified by the higher (up to 0.20e) values of global electron density transfer for Cr(CO)3-coordinated transition states. Electron localization function analysis along the exo/ortho reaction path reveals the non-concerted mechanism in the formation of a new bond with the initial appearance of a C–C single bond followed by the O–C one.

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On the Nature of Catastrophe Unfoldings Along the Diels–Alder Cycloaddition Pathway

Ayarde‐Henríquez,

Guerra,

Duque‐Noreña

et al. 2024

Electron Density

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Topological unraveling of the [3+2] cycloaddition (32CA) reaction between N-methylphenylnitrone and styrene catalyzed by the chromium tricarbonyl complex using electron localization function and catastrophe theory

Abstract: We have investigated the reaction mechanisms of [3+2] cycloaddition (32CA) between N-methylphenylnitrone and styrene catalyzed by chromium tricarbonyl complex at the MPWB1K/6-311G(d,p) level of approximation. Activation energy analysis reveals that...

Cited by 7 publications

References 50 publications

Deciphering the Molecular Mechanism of Intramolecular Reactions from the Perspective of Bonding Evolution Theory

Deciphering the Molecular Mechanism of Intramolecular Reactions from the Perspective of Bonding Evolution Theory

How a Chromium Tricarbonyl Complex Catalyzes the [3 + 2] Cycloaddition Reaction of N-Substituted Phenylnitrones with Styrene: A Molecular Electron Density Theory Analysis

On the Nature of Catastrophe Unfoldings Along the Diels–Alder Cycloaddition Pathway

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