Aromatic reactivity revealed: beyond resonance theory and frontier orbitals

Brown, James; Cockroft, Scott L.

doi:10.1039/c3sc50309g

Cited by 47 publications

(48 citation statements)

References 55 publications

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“…In each case, the lowest

\overset{I}{true}

S,min are found over the positions that are most prone to react with an electrophile, that is, the meta directing versus ortho–para directing tendencies of nitrobenzene and aniline, respectively, are reproduced by the

\overset{I}{true}

S,min positions . Furthermore, the magnitude of the

\overset{I}{true}

S,min at the reactive site reflects the relative reactivity at that site, and allows for the ranking of different molecules with respect to their rate constants in, for example, the S E Ar reaction . In the case of aniline, there is also an

\overset{I}{true}

S,min at the nitrogen that reflects its nucleophilicity and basicity.…”

Section: Molecular Surface Propertiesmentioning

confidence: 99%

“…Studies by Liljenberg et al. and Brown and Cockroft have shown that

\overset{I}{true}

S ( r ) is capable of quantitatively predicting regioselectivity and relative reactivity also of more complex molecules, including heteroaromatic systems with multiple rings . Whereas the method generally works also in problematic cases where resonance theory or frontier molecular orbital (FMO) theory fail, it does have problems in systems with sterically hindered interaction sites.…”

Section: Molecular Surface Propertiesmentioning

confidence: 99%

“…Such problems are more frequent when the electrophile is large and bulky, as in Friedel–Craft acylations .

\overset{I}{true}

S ( r ) has been shown to be highly accurate also for predicting the reactivity of kinetically controlled electrophilic reactions other than S E Ar, such as electrophilic addition reactions and transmetalation reactions …”

Section: Molecular Surface Propertiesmentioning

confidence: 99%

See 2 more Smart Citations

The Molecular Surface Property Approach: A Guide to Chemical Interactions in Chemistry, Medicine, and Material Science

Brinck

Stenlid

2018

Advcd Theory and Sims

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The current status of the molecular surface property approach (MSPA) and its application for analysis and prediction of intermolecular interactions, including chemical reactivity, are reviewed. The MSPA allows for identification and characterization of all potential interaction sites of a molecule or nanoparticle by the computation of one or more molecular properties on an electronic isodensity surface. A wide range of interactions can be analyzed by three properties, which are well-defined within Kohn-Sham density functional theory. These are the electrostatic potential, the average local ionization energy, and the local electron attachment energy. The latter two do not only reflect the electrostatic contribution to a chemical interaction, but also the contributions from polarization and charge transfer. It is demonstrated that the MSPA has a high predictive capacity for non-covalent interactions, for example, hydrogen and halogen bonding, as well as organic substitution and addition reactions. The latter results open up applications within drug design and medicinal chemistry. The application of MSPA has recently been extended to nanoparticles and extended surfaces of metals and metal oxides. In particular, nanostructural effects on the catalytic properties of noble metals are rationalized. The potential for using MSPA in rational design of heterogeneous catalysts is discussed. Tore Brinck is professor of physical chemistry at KTH Royal Institute of Technology in Stockholm, Sweden. He received his M.Sc. in chemical engineering from KTH in 1990, and his Ph.D. from the University of New Orleans in 1993 with Prof. Peter Politzer as Ph.D. advisor. His research involves the development of electronic descriptors for the analysis of chemical reactivity, as well as the application of electronic structure methods to the analysis of chemical reactions in condensed phases. He also uses computational chemistry to study enzyme design, heterogeneous catalysis, and energetic materials. Joakim Halldin Stenlid is a postdoctoral fellow in the group of Prof. Lars GM Pettersson at Stockholm University where he is carrying out computational studies in electrochemistry and heterogeneous catalysis. He obtained his Ph.D. in physical chemistry from KTH

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“…In each case, the lowest

\overset{I}{true}

\overset{I}{true}

S,min positions . Furthermore, the magnitude of the

\overset{I}{true}

\overset{I}{true}

S,min at the nitrogen that reflects its nucleophilicity and basicity.…”

Section: Molecular Surface Propertiesmentioning

confidence: 99%

“…Studies by Liljenberg et al. and Brown and Cockroft have shown that

\overset{I}{true}

Section: Molecular Surface Propertiesmentioning

confidence: 99%

“…Such problems are more frequent when the electrophile is large and bulky, as in Friedel–Craft acylations .

\overset{I}{true}

Section: Molecular Surface Propertiesmentioning

confidence: 99%

See 1 more Smart Citation

The Molecular Surface Property Approach: A Guide to Chemical Interactions in Chemistry, Medicine, and Material Science

Brinck

Stenlid

2018

Advcd Theory and Sims

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show abstract

“…Computed average local ionization energies (ALIEs) were recently shown by Brown et al. to be quantitative predictors of the nucleophilicities of aromatic molecules in cases in which steric influences can be neglected 28. In addition, we reported recently that ALIEs are excellent predictors for the regioselectivity of the reduction of chlorins 27b.…”

Section: Resultsmentioning

confidence: 93%

Indachlorins: Nonplanar Indanone‐Annulated Chlorin Analogues with Panchromatic Absorption Spectra between 300 and 900 nm

Samankumara

Dorazio

Akhigbe

et al. 2015

Chemistry A European J

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Indaphyrins, pyrrole-modified porphyrins containing a cleaved pyrrole β,β'-bond and two annulated indanone moieties, possess unusually broadened and redshifted UV/Vis spectra because of their π-expanded chromophores. The parent free base indaphyrin has been crystallographically characterized, highlighting its strongly ruffled conformation incorporating a helimeric twist. It was shown to be susceptible to regiospecific derivatizations at the opposite side of the ring-cleaved pyrrole (dihydroxylation, followed by functional group transformations of the resulting diol functionality), generating indaphyrin-based chlorin analogues, indachlorins, that incorporate a dihydroxypyrroline, pyrrolindione, oxazolone, or a morpholine moiety. Structural modifications resulted in further broadening and hyper- and bathochromic shifts of the optical spectra, some of which possess a nearly panchromatic absorption between 300 to well above 900 nm. The extents to which these modifications affect their solid-state conformations were analyzed.

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“…Over time, several cases where FMO fails to predict reactivity, for example, electrophilic aromatic substitution reactions have been reported . It has been recognized that the reactivity of these systems is not determined only by the HOMO or LUMO but one or more different orbitals take place in the response to the reagent (under perturbation) .…”

Section: Introductionmentioning

confidence: 99%

Proposal of a simple and effective local reactivity descriptor through a topological analysis of an orbital‐weighted fukui function

et al. 2017

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The prediction of reactivity is one of the long-standing objectives of chemistry, contributing to enforce the link between theory and experiment. In particular, the regioselectivity of aromatic molecules has motivated the proposal of different reactivity descriptors based on foundational theories, like Frontier Molecular Orbital (FMO) theory and density functional theory, to predict and rationalize such regioselectivity. This article examines cases where reactivity descriptors, based on FMO theories, are known to have failed, specifically on electrophilic aromatic substitution reactions, through a simple but effective new reactivity model: the Orbital-weighted Fukui function ( fw-(r)) and its topological analysis. Interestingly, this descriptor proves to be effective in adequately predicting regioselectivities where other approximations failed. © 2017 Wiley Periodicals, Inc.

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Aromatic reactivity revealed: beyond resonance theory and frontier orbitals

Abstract: Ionisation energy surfaces consistently reveal the most reactive sites in aromatic molecules even where established reactivity models fail. Post-print of a peer-reviewed article published by the Royal Society of Chemistry.

Cited by 47 publications

References 55 publications

The Molecular Surface Property Approach: A Guide to Chemical Interactions in Chemistry, Medicine, and Material Science

The Molecular Surface Property Approach: A Guide to Chemical Interactions in Chemistry, Medicine, and Material Science

Indachlorins: Nonplanar Indanone‐Annulated Chlorin Analogues with Panchromatic Absorption Spectra between 300 and 900 nm

Proposal of a simple and effective local reactivity descriptor through a topological analysis of an orbital‐weighted fukui function

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