The principle of maximum hardness and structural effects of nonbonded interactions in chloronitromethanes

Politzer, Peter; Murray, Jane S.; Macaveiu, Laura

doi:10.1016/j.theochem.2009.10.012

Journal of Molecular Structure: THEOCHEM

2010

DOI: 10.1016/j.theochem.2009.10.012

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The principle of maximum hardness and structural effects of nonbonded interactions in chloronitromethanes

Peter Politzer

Jane S. Murray

Laura Macaveiu

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Cited by 5 publications

(1 citation statement)

References 34 publications

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“…Besides, we have attempted to rationalize the mechanisms thanks to conceptual DFT descriptors such as the chemical potential, the hardness, the Fukui functions and the electrophilicity index [20][21][22][23][24][25]. These approaches have been rather successful to predict the products of such reactions [26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45]. The present paper is then organized as follows: In a first section, computational details are given to introduce the reactivity indexes used in the present work.…”

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confidence: 99%

Allylation of active methylene compounds with cyclic Baylis–Hillman alcohols: a DFT study

Harrath

Essalah²,

Morell

et al. 2015

Theor Chem Acc

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International audienceAllylation reaction of active methylene compounds with cyclic Baylis–Hillman (BH) alcohol catalyzed by 4-dimethyamino-pyridine (DMAP) has been investigated by means of density functional theory with B3LYP/6-311++G(d,p). The first step on the chemical path is considered as an acid–base reaction. It is then followed by allylation of active methylene compound with cyclic BH alcohol. Calculated gas-phase pKa values illustrate that active methylene compounds have higher acidity than the considered cyclic BH alcohol. The DMAP catalytic activity may be interpreted as a proton transfer bridge between the active methylene compounds and the cyclic BH alcohol. Two alternative competing reactivity sites are present. Regioselectivity has been carried out on the base of natural atomic charge, Fukui index. The computations help rationalizing the fact that the direct allylation is the favored reaction and leads to the end-product

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mentioning

confidence: 99%

Allylation of active methylene compounds with cyclic Baylis–Hillman alcohols: a DFT study

Harrath

Essalah²,

Morell

et al. 2015

Theor Chem Acc

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DFT studies on hydrogen-bonding, Stacking, and XH···π-Bonded systems in presence of external electric field

Dutta

Bhattacharyya

2015

Int. J. Quantum Chem.

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Effect of external electric field on interaction energy as well as stability of the hydrogen-bonding, stacking, and OAHÁ Á Ápbonded systems are analyzed in the light of density functional theory (DFT) and conceptual DFT. Interaction energy and stability measured in terms of global hardness and highest occupied molecular orbital energy of the considered systems are observed to be sensitive toward the strength and direction of the applied external electric field. The curvature of the potential energy surfaces gets changed in presence of an external electric field.

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ETS-NOCV description of σ-hole bonding

2012

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The ETS-NOCV analysis was applied to describe the σ-hole in a systematic way in a series of halogen compounds, CF3-X (X = I, Br, Cl, F), CH3I, and C(CH3)nH3-n-I (n = 1,2,3), as well as for the example germanium-based systems. GeXH3, X = F, Cl, H. Further, the ETS-NOCV analysis was used to characterize bonding with ammonia for these systems. The results show that the dominating contribution to the deformation density, Δρ1, exhibits the negative-value area with a minimum, corresponding to σ-hole. The “size” (spatial extension of negative value) and “depth” (minium value) of the σ-hole varies for different X in CF3-X, and is influenced by the carbon substituents (fluorine atoms, hydrogen atoms, methyl groups). The size and depth of σ-hole decreases in the order: I, Br, Cl, F in CF3-X. In CH3-I and C(CH3)nH3-n-I, compared to CF3-I, introduction of hydrogen atoms and their subsequent replacements by methyl groups lead to the systematic decrease in the σ-hole size and depth. The ETS-NOCV σ-hole picture is consistent with the existence the positive MEP area at the extension of σ-hole generating bond. Finally, the NOCV deformation density contours as well as by the ETS orbital-interaction energy indicate that the σ-hole-based bond with ammonia contains a degree of covalent contribution. In all analyzed systems, it was found that the electrostatic energy is approximately two times larger than the orbital-interaction term, confirming the indisputable role of the electrostatic stabilization in halogen bonding and σ-hole bonding.FigureGraphical representation of the σ-hole on the halogen atom, based on the molecular electrostatic potential (upper row) and the NOCV deformation-density channel Δρ1 (lower row and the right-hand side plot)

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The principle of maximum hardness and structural effects of nonbonded interactions in chloronitromethanes

Cited by 5 publications

References 34 publications

Allylation of active methylene compounds with cyclic Baylis–Hillman alcohols: a DFT study

Allylation of active methylene compounds with cyclic Baylis–Hillman alcohols: a DFT study

DFT studies on hydrogen-bonding, Stacking, and XH···π-Bonded systems in presence of external electric field

ETS-NOCV description of σ-hole bonding

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