Applications of the Conceptual Density Functional Theory Indices to Organic Chemistry Reactivity

Domingo, Luís R.; Ríos‐Gutiérrez, Mar; Pérez, Patricia

doi:10.3390/molecules21060748

Cited by 957 publications

(863 citation statements)

References 64 publications

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“…CDFT [23,24] provides different indices to rationalise and understand chemical structure and reactivity. The global electrophilicity index [48] ω, is given by the following expression, , in terms of the electronic chemical potential and the chemical hardness .…”

Section: Methodsmentioning

confidence: 99%

“…Global reactivity indices defined within CDFT [23,24] are powerful tools to explain the reactivity in cycloaddition reactions. Since the global electrophilicity and nucleophilicity scales are given at the B3LYP/6-31G(d) level, the present analysis has been performed at this computational level.…”

Section: Analysis Of the Cdft Reactivity Indices At The Gs Of The Reamentioning

confidence: 99%

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A Molecular Electron Density Theory Study of the Reactivity of Azomethine Imine in [3+2] Cycloaddition Reactions

Domingo

Ríos‐Gutiérrez

2017

Preprint

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Abstract:The electronic structure and the participation of the simplest azomethine imine (AI) in [3+2] cycloaddition (32CA) reactions have been analysed within the Molecular Electron Density Theory (MEDT) using DFT calculations at the MPWB1K/6-311G(d) level. Electron localisation function (ELF) topological analysis reveals that AI has a pseudoradical structure, while the conceptual DFT reactivity indices characterise this TAC as a moderate electrophile and a good nucleophile. The non-polar 32CA reaction of AI with ethylene takes place through a one-step mechanism with low activation energy, 5.3 kcal/mol -1 . A bonding evolution theory (BET) study indicates that this reaction takes place through a non-concerted [2n+2τ] mechanism in which the C−C bond formation is clearly anticipated prior to the C−N one. On the other hand, the polar 32CA reaction of AI with dicyanoethylene takes place through a two-stage one-step mechanism. Now, the more favourable regioisomeric transition state structure (TS) is located 8.5 kcal·mol -1 below the reagents, in complete agreement with the high polar character of the TS. The current MEDT study makes it possible to extend Domingo's classification of 32CA reactions to a new pra-type of reactivity.

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Section: Methodsmentioning

confidence: 99%

Section: Analysis Of the Cdft Reactivity Indices At The Gs Of The Reamentioning

confidence: 99%

A Molecular Electron Density Theory Study of the Reactivity of Azomethine Imine in [3+2] Cycloaddition Reactions

Domingo

Ríos‐Gutiérrez

2017

Preprint

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“…The ASD over each atom of the radical cation and radical anion of the molecule gives the local nucleophilic P k − and electrophilic P k + Parr functions of the neutral molecule [23].…”

Section: Molecular Modeling Of the Structures Properties And Glycatimentioning

confidence: 99%

Molecular Modeling of the Structures, Properties and Glycating Power of Some Reducing Disaccharides

Mitnik

Frau

2017

MOJDDT

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The molecular structures, properties and glycating power of some reducing disaccharides (Cellobiose, Gentiobiose, Isomaltose, Lactose, Laminaribiose, Maltose, Mannobiose and Xylobiose) have been studied by resorting to Chemical Reactivity Theory including Conceptual DFT and Molecular Electron Density Theory (MEDT). The reactivity sites for nucleophilic and electrophilic attacks have been chosen by relating them to the Fukui function indices, the condensed dual descriptor ∆f(r) and the Parr functions. The glycating power of the reducing disaccharides is compared with that of simple hexoses and pentoses through the values of the calculated reactivity descriptors. Keywords: Molecular Modeling of the Structures, Properties and Glycating Power of Some Reducing Disaccharides 2/14Copyright: ©2017 Frau et al.Using a finite difference approximation and the "Koopmans in DFT" procedure (KID) , the former expressions can be written as: (3) (4) where H ε and L ε are the highest occupied and the lowest unoccupied molecular orbitals, HOMO and LUMO, respectively. In turn, the electrophilicity index ω has been defined as [17]:(5) The condensed Fukui functions can be employed to determine the reactivity of each atom in the molecule. The corresponding condensed functions are given by (6) (For nucleophilic attack),(for electrophilic attack), and (8) (for radical attack), where q K is the gross charge of atom k in the molecule.The condensed dual descriptor has been defined as [18,19]:From the interpretation given to the Fukui function, one can note that the sign of the dual descriptor is very important to characterize the reactivity of a site within a molecule toward a nucleophilic or an electrophilic attack. That is, if (10) Then the site is favored for a nucleophilic attack, whereas if (11) Then the site may be favored for an electrophilic attack [18][19][20].In 2013, Domingo proposed the Parr functions P(r) [21,22] which are given by the following equations:(12) (for electrophilic attacks) and (13) (for nucleophilic attacks) which are related to the atomic spin density (ASD) at the r atom of the radical cation or anion of a given molecule, respectively. The ASD over each atom of the radical cation and radical anion of the molecule gives the local nucleophilic P k − and electrophilic P k + Parr functions of the neutral molecule [23]. Settings and computational methodsFollowing the lines of our previous work and it has been described in detail before, [8][9][10][11][12][13][14] all computational studies were performed with the Gaussian 09 [24] series of programs with density functional methods as implemented in the computational package. The equilibrium geometries of the molecules were determined by means of the gradient technique. The force constants and vibrational frequencies were determined by computing analytical frequencies on the stationary points obtained after the optimization to check if there were true minima. The basis set used in this work was Def2SVP for geometry optimization and frequencies while Def2TZVP ...

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“…The most relevant indices defined within the conceptual DFT [33] for the study of the organic reactivity are discussed elsewhere [35][36][37][38][39]. Molecular reactivity indices [35][36][37][38][39] …”

Section: Molecular Reactivitiesmentioning

confidence: 99%

“…In the present study, quantum chemical computations will be performed within DFT using WB97XD/6-31G(d) model to investigate the molecular structure, IR, and NMR of the newly synthetized molecules [32][33][34][35][36][37][38]. X-ray crystallographic data of 3B will be obtained and used to support 2 Journal of Chemistry and verify the theoretical results.…”

Section: Introductionmentioning

confidence: 99%

Novel Thiazole Derivatives of Medicinal Potential: Synthesis and Modeling

El‐Sattar

El‐Naggar

Abdel‐Mottaleb

2017

Journal of Chemistry

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This paper reports on the synthesis of new thiazole derivatives that could be profitably exploited in medical treatment of tumors. Molecular electronic structures have been modeled within density function theory (DFT) framework. Reactivity indices obtained from the frontier orbital energies as well as electrostatic potential energy maps are discussed and correlated with the molecular structure. X-ray crystallographic data of one of the new compounds is measured and used to support and verify the theoretical results.

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Applications of the Conceptual Density Functional Theory Indices to Organic Chemistry Reactivity

Cited by 957 publications

References 64 publications

A Molecular Electron Density Theory Study of the Reactivity of Azomethine Imine in [3+2] Cycloaddition Reactions

A Molecular Electron Density Theory Study of the Reactivity of Azomethine Imine in [3+2] Cycloaddition Reactions

Molecular Modeling of the Structures, Properties and Glycating Power of Some Reducing Disaccharides

Novel Thiazole Derivatives of Medicinal Potential: Synthesis and Modeling

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