Studies on the charge density distribution in p-substituted phenylnitrenium cation

• Autorzy: Przybyłek M.

Warianty tytułu

PL

Badania nad rozkładem gęstości ładunku w p-podstawionym kationie fenylonitreniowym

• Języki publikacji: EN

Abstrakty

EN

Aniline and its derivatives are known to be mutagenic. This activity is caused by the formation of phenylnitrenium cations during aniline oxidation. Reactivity of the positively charged chemical species can be measured by means of s+ substituent constant. In this paper charge density distribution in p-substituted nitrenium cations and reactivity indices such as, hardness η, electronegativity χ , and electrophilicily ω were analyzed. In order to evaluate which parameters are the most appropriate in describing electron density, correlation coefficients with s+ were calculated. The best results were achieved in case of energy of the lowest unoccupied molecular orbital (ELUMO). NBO lone pair orbital energy NBO ELP, and partial charge on the nitrenium nitrogen calculated using NBO method. NBO N charge. Analysis of these parameters showed that values of s+ depends strongly on the charge density on nitrenium nitrogen atom. According to NBO calculations. electron density on C-2 and C-6 (atoms numeration according to Fig. 1) is lower than in case of C-3 and C-5. These facts are consistent with the resonance theory.

PL

Anilina i jej pochodne wykazują właściwości mutageniczne. Ta aktywność wywołana jest powstawaniem kationu fenylonitreniowego podczas utleniania aniliny. W niniejszej publikacji, zbadana została dystrybucja gęstości ładunku w p-podstawionym kationie fenylonitreniowym. Przeanalizowano, wartości indeksów reaktywności, takich jak twardość η, elektroujemność χ, elektrofilowość ω oraz wartości ładunków Mullikena, NBO. CHelpG i APT. Aby stwierdzić które parametry są najlepsze do oceny gęstości elektronowej obliczono współczynniki korelacji dla tych parametrów z wartościami stałych podstawnika sp+. Najlepsze rezultaty uzyskano w przypadku energii poziomu LUMO, energii orbitaluwolnej pary elektronowej i ładunku NBO na nitreniowym atomie azotu. Analizy tych parametrów wykazały, że wartość stałej sp+ jest silnie uzależniona od gęstości ładunku na nitreniowym atomie azotu. Na podstawie obliczeń NBO stwierdzono, że gęstość elektronowa na atomach C-2 i C-6 jest mniejsza niż w przypadku C-3 i C-5. Przedstawione powyżej fakty są zgodne z teorią rezonansu.

Słowa kluczowe

EN

reactivity; mutagenicity; population analysis; aromatic

PL

efekt podstawnikowy; reaktywność; mutageniczność; analiza populacyjna; aromatyczność

• Wydawca: Bydgoskie Towarzystwo Naukowe
• Czasopismo: Ekologia i Technika
• Rocznik: 2013
• Tom: R. 21, nr 5
• Strony: 230--236
• Opis fizyczny: Bibliogr. 36 poz., tab.

Twórcy

autor

Przybyłek M.

• Nicolaus Copernicus University, Collegium Medicum.,Department of Physical Chemistry

Bibliografia

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