O zależnościach pomiędzy aromatycznością i efektem podstawnikowym w układach jednopierścieniowych

Szatyłowicz, Halina; Krygowski, Tadeusz Marek

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Tytuł artykułu

O zależnościach pomiędzy aromatycznością i efektem podstawnikowym w układach jednopierścieniowych

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Szatyłowicz Halina , Krygowski Tadeusz Marek

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Warianty tytułu

On relation between substituent effect and aromaticity in monocyclic systems

Języki publikacji

Abstrakty

Aromaticity/aromatic and substituent/substituent effects belong to the most commonly used terms in organic chemistry and related fields. They are used for more than a century, and so far are the subject of thousands publications a year. The quantitative description of the aromaticity of planar π-electron cyclic molecules is based on four criteria: (i) they are more stable than their acyclic unsaturated analogues, (ii) bonds have intermediate lengths between those for the single and double ones, (iii) external magnetic field induces π-electron ring current, and (iv) aromatic systems prefer reactions in which the π-electron structure is preserved. conserved. Quantitative characteristics based on these criteria, named as aromaticity indices, allow to relate aromaticity to the substituent effect. This latter can be described using either traditional Hammett-type substituent constants or characteristics based on quantum-chemistry. For this purpose, the energies of properly designed homodesmotic reactions and electron density distribution are used. In the first case, a descriptor named SESE (substituent effect stabilization energy) is obtained, while in the second case – cSAR (charge of the substituent active region), which is the sum of the charge of the ipso carbon atom and the charge of the substituent. The application of these substituent effect descriptors to a set of π-electron systems, such as: benzene, quinones, cyclopenta- and cyclohepta-dienes, as well as some azoles, allowed to draw the following conclusions: (i) The less aromatic the system, the stronger the substituent influences the π-electron system. Highly aromatic systems are resistant to the substituent effect, in line with the organic chemistry experience that aromatic compounds dislike reactions leading to changes in the π-electron structure of the ring. (ii) Intramolecular charge transfer (resonance effect) is privileged in cases where the number of bonds between the electron-attracting and electron-donating atoms is even. These effects are much weaker when this number is odd. Classically, it may be related to traditional para vs meta substituent effects in benzene derivatives. We should note that in electron-accepting groups, such as CN or NO₂ (and others), electron-accepting atoms are second counting from Cipso. (iii) In all cases, when the substituent changes number of π-electrons in the ring in the direction of 4N+2, its aromaticity increases, for example electron-donating substituents in exocyclic substituted pentafulvene, or a halogen atom in complexes with heptafulvene.

Słowa kluczowe

aromatyczność HOMA NICS efekt podstawnikowy stałe Hammetta metody chemii kwantowej

aromaticity HOMA harmonic oscillator model of aromaticity NICS nucleus independent chemical shift substituent effect Hammett constants quantum chemistry modeling

Wydawca

Polskie Towarzystwo Chemiczne

Czasopismo

Wiadomości Chemiczne

Rocznik

2019

Tom

[Z] 73, 3-4

Strony

243--261

Opis fizyczny

Bibliogr. 86 poz., schem., wykr.

Twórcy

autor

Szatyłowicz Halina

halina@ch.pw.edu.pl

Wydział Chemiczny Politechniki Warszawskiej, ul. Noakowskiego 3, 00-664 Warszawa

autor

Krygowski Tadeusz Marek

tmktyg@chem.uw.edu.pl

Wydział Chemii Uniwersytetu Warszawskieg,o ul. Pasteura 1, 02-093 Warszawa

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Uwagi

Opracowanie rekordu w ramach umowy 509/P-DUN/2018 ze środków MNiSW przeznaczonych na działalność upowszechniającą naukę (2019).

Typ dokumentu

Bibliografia

Identyfikator YADDA

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