Understanding the Molecular Mechanism of the Rearrangement of Internal Nitronic Ester into Nitronorbornene in Light of the MEDT Study

Kącka‐Zych, Agnieszka

doi:10.3390/molecules24030462

Cited by 18 publications

(7 citation statements)

References 57 publications

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“…ELF localization domains were represented by using the ParaView software at an isovalue of 0.75 a.u [42,43]. A similar approach has been successfully used to explain the mechanism of different types of reactions [44][45][46][47][48][49][50].…”

Section: Computational Detailsmentioning

confidence: 99%

Perfluorobicyclo[2.2.0]hex-1(4)-ene as unique partner for Diels–Alder reactions with benzene: a density functional theory study

Kącka‐Zych

Pérez

2021

Theor Chem Acc

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The mechanism of the Diels–Alder reactions between perfluorobicyclo[2.2.0]hex-1(4)-ene (1a) and bicyclo[2.2.0]hex-1(4)-ene (1b) with benzene (2a) and naphthalene (2b) has been studied within the density functional theory at the MPWB1K/6-311G(d,p) level. The bonding pattern in these reactions is analyzed in the topology of the electron localization function within the bonding evolution theory perspective. The bonding electron density changes along the reaction paths reveal that the C–C bond formation takes place through a synchronous and non-concerted one-step mechanism and proceeds with a moderate activation energy. The reactivity order with 1a is 2a–2b. The reactions begin by the rupture of the double bond in the strained 1a-b molecules, and then two pseudoradical centers at the 1a-b fragments are created. Finally, at the same time, two new single bonds are formed in the cycloaddition products. The TSs proceed with high global electron density transfer providing a polar character at these reactions.

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Section: Computational Detailsmentioning

confidence: 99%

Perfluorobicyclo[2.2.0]hex-1(4)-ene as unique partner for Diels–Alder reactions with benzene: a density functional theory study

Kącka‐Zych

Pérez

2021

Theor Chem Acc

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“…This method, as we have proven, it's the most powerful instrument for studying and understanding the molecular mechanism of various types of reactions. [30][31][32][33][34][35][36][37] 2 | COMPUTATIONAL METHODS…”

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confidence: 99%

Understanding the uniqueness of the stepwise [4 + 1] cycloaddition reaction between conjugated nitroalkenes and electrophilic carbene systems with a molecular electron density theory perspective

Kącka‐Zych

2020

Int J of Quantum Chemistry

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The [4 + 1] cycloaddition (41CA) and [2 + 1] cycloaddition (21CA) reactions of the α-halogeno-nitroalkenes with carbene have been studied using the molecular electron density theory through density functional theory calculations at the MPWB1K(PCM)/ 6-311G(d,p) computational level. The 41CA reaction take place through a polar twostep mechanism involving the formation of a zwitterionic intermediate. The competitive 21CA reaction path proceeds according to nonconcerted two-stage one-step. Bonding evolution theory analysis of 41CA reaction allows the distinguishing of four groups along the reaction path. The reaction begins with rupture of the C C double bond of the alkene moiety and formation of the pseudoradical center. Formation of the O C and C C new single bonds begins in subsequent phases. In the last stage of the 41CA reaction path, we observed the formation of an N C new double bond. In the case of 21CA reaction path, we observed the successive rupture of the C C double bond of the alkene moiety, formation of C C new single bond and pseudoradical center, and creation of a second C C single bond.

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“…The polarity of the reaction environment was simulated using a relatively simple self-consistent reaction field (SCRF) [ 37 , 38 , 39 ] based on the polarizable continuum model (PCM) of Tomasi’s group [ 40 , 41 ]. A close enough approach to analyzing other many different reactions have been used successfully in many other works [ 4 , 42 , 43 , 44 , 45 , 46 ]. The topological analyses of the electron localization function (ELF) [ 47 , 48 , 49 ] were performed with the TopMod [ 50 ].…”

Section: Methodsmentioning

confidence: 99%

Experimental and Theoretical Mechanistic Study on the Thermal Decomposition of 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline

et al. 2021

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The present paper is a continuation of comprehensive study regarding to synthesis and properties of pyrazoles and their derivatives. In its framework an experimental and theoretical studies of thermal decomposition of the 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline were performed. It was found, that the decompositions of the mentioned pyrazoline system in the solution and at the melted state proceed via completely different molecular mechanisms. These mechanisms have been explained in the framework of the Molecular Electron Density Theory (MEDT) with the computational level of B3LYP/6-31G(d). A Bonding Evolution Theory (BET) examination of dehydrochlorination of the 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline permits elucidation of the molecular mechanism. It was found, that on the contrary for most known HCl extrusion processes in solution, this reaction is realised via single-step mechanism.

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Understanding the Molecular Mechanism of the Rearrangement of Internal Nitronic Ester into Nitronorbornene in Light of the MEDT Study

Cited by 18 publications

References 57 publications

Perfluorobicyclo[2.2.0]hex-1(4)-ene as unique partner for Diels–Alder reactions with benzene: a density functional theory study

Perfluorobicyclo[2.2.0]hex-1(4)-ene as unique partner for Diels–Alder reactions with benzene: a density functional theory study

Understanding the uniqueness of the stepwise [4 + 1] cycloaddition reaction between conjugated nitroalkenes and electrophilic carbene systems with a molecular electron density theory perspective

Experimental and Theoretical Mechanistic Study on the Thermal Decomposition of 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline

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