A Conceptual DFT Study of the Chemical Reactivity of Magnesium Octaethylporphyrin (MgOEP) as Predicted by the Minnesota Family of Density Functionals

The M06 family of density functionals has been assessed for the calculation of the molecular structure and properties of the Naringin molecule. The chemical reactivity descriptors have been calculated through Conceptual DFT. The active sites for nucleophilic and electrophilic attacks have been chosen by relating them to the Fukui function indices and the dual descriptorf(2)(r). A comparison between the descriptors calculated through vertical energy values and those arising from the Koopmans' theorem approximation has been performed in order to check for the validity of the last procedure.

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DFT study of the stereo-selectivity of oxygenated heterocycles from 10 to 12 links

Canadian Journal of Chemistry ◽

10.1139/cjc-2012-0521 ◽

2013 ◽

Vol 91 (9) ◽

pp. 811-820

Author(s):

Hafida Merouani ◽

Christophe Morell ◽

Nadia Ouddai ◽

Henry Chermette

Keyword(s):

Experimental Evidence ◽

Chemical Reactivity ◽

Diels Alder ◽

Conceptual Dft ◽

Dft Study ◽

Electronic Effects ◽

Transition Structure ◽

Dual Descriptor ◽

Ring Strain ◽

Stereo Selectivity

Intra-molecular Diels–Alder (IMDA) reactions of tethered trienes can furnish two distinct diastereoisomeric products, the cis (i.e., endo) stereoisomer and the trans (i.e., exo) stereoisomer. Experimental evidence shows a quite high cis stereo-selectivity for 10-link compounds (cis/trans = 70:30), while 11- and 12-links compounds exhibit no particular selectivity. DFT (B3LYP/6-31G*) computations provide useful insights into the origins of this amazing stereo-selectivity. The cyclization path towards trans stereo-isomer is always thermodynamically favored, whatever the size of the system. The high cis stereo-selectivity displayed by the 10-link system is kinetically controlled by a tug-of-war between ring strain and electronic effects in the transition structure. The dual descriptor of chemical reactivity, a conceptual DFT based descriptor designed to delineate electronic effects, has been used to unravel the stabilizing processes that take place at the TSs.

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Application of DFT concepts to the study of the chemical reactivity of some resveratrol derivatives through the assessment of the validity of the “Koopmans in DFT” (KID) procedure

Journal of Theoretical and Computational Chemistry ◽

10.1142/s0219633617500067 ◽

2017 ◽

Vol 16 (01) ◽

pp. 1750006 ◽

Cited By ~ 5

Author(s):

Juan Frau ◽

Francisco Muñoz ◽

Daniel Glossman-Mitnik

Keyword(s):

Chemical Reactivity ◽

Great Accuracy ◽

Conceptual Dft ◽

Neutral System ◽

Density Functionals ◽

Reactivity Descriptors ◽

Homo And Lumo ◽

Resveratrol Derivatives ◽

Cis And Trans

The validity of the “Koopmans in DFT” (KID) procedure have been assessed by means of the calculation of several Conceptual DFT reactivity descriptors calculated through a [Formula: see text]SCF procedure compared with the results of the HOMO and LUMO energies of the neutral system. Three resveratrol derivatives were considered: cis- and trans-piceid and resveratrone-6-O-[Formula: see text] glucoside. The Minnesota latest family of density functionals have been considered for the calculations in connection with water as a solvent simulated with the SMD parametrization. It is shown that the range-separated hybrids MN12SX and N12SX fulfill the KID procedure with great accuracy.

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