A DFT Study of the Cheletropic Reaction between Diacetyl and Trimethylphosphite
محل انتشار: بیست و ششمین سمینار شیمی آلی ایران
سال انتشار: 1397
نوع سند: مقاله کنفرانسی
زبان: انگلیسی
مشاهده: 347
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شناسه ملی سند علمی:
ISOC26_095
تاریخ نمایه سازی: 2 شهریور 1398
چکیده مقاله:
The mechanism of the cheletropic reaction between diacetyl and trimethylphosphite has beenstudied by density functional-based hybrid functional M062x with 6-31+G(d,p) basis set [1,2]. The ground and transition states were confirmed by the frequency calculations. The rateconstants and activation energies of this reaction is 12.71×10-11 M-1s-1 and 22.26 kcalmol-1.The global reactivity index analysis was performed for the related reactants. The frontier molecularorbital (FMO) analysis allowed us to understand the nature of these [4 + 2] cycloaddition.An analysis of the FMO for diacetyl and trimethylphosphite indicated that the most favorableinteraction along the cycloaddition process takes place between HOMO trimethylphosphiteand LUMO diacetyl, the energy gap was 7.22 eV. A good electrophile wascharacterized by a low value of chemical potential (μ) and hardness (η) and high value of ω.The μ, η and ω for diacetyl (-4.86, 8.77, 1.56) and trimethylphosphite (-3.90, 7.59, 0.87) isshown that diactyl is electrophile. The trimethylphosphite and diactylewas classified as marginaland moderate electrophile within the electrophilicity scale [3]. The Δω for the reactionhad a low value (0.68 eV), thus indicating that the corresponding cycloaddition will have alow polar character.
نویسندگان
Ameneh Tanotas
Department of Chemistry, Faculty of Science, University of Sistan and Baluchestan, Zahedan, Iran
Mariya Dehvari
Department of Chemistry, Faculty of Science, University of Sistan and Baluchestan, Zahedan, Iran
Mehdi Shahraki
Department of Chemistry, Faculty of Science, University of Sistan and Baluchestan, Zahedan, Iran
Mahdieh Darijani
Department of Chemistry, Faculty of Science, University of Sistan and Baluchestan, Zahedan, Iran