کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
5418002 | 1506959 | 2007 | 11 صفحه PDF | دانلود رایگان |
عنوان انگلیسی مقاله ISI
Bonding and aromaticity of cyclic phosphazenes viewed as interaction of Dnh fragments
دانلود مقاله + سفارش ترجمه
دانلود مقاله ISI انگلیسی
رایگان برای ایرانیان
کلمات کلیدی
موضوعات مرتبط
مهندسی و علوم پایه
شیمی
شیمی تئوریک و عملی
پیش نمایش صفحه اول مقاله
چکیده انگلیسی
The qualitative molecular orbital approach based on orbital interactions was used to explore the nature of bonding in cyclic fluorophosphazenes (F2PN)n, where n is 2-6. Besides the classical skeleton of Ï-bonds, only two, one radial and one axial, 2n-center two-electron Ï-bonds significantly participate in the extra stabilization of the (PN)n ring. The Ï-radial interaction is more effective and comparable by size with the Ï ones. Additional slight stabilization of a (PN)n ring is achieved by nonbonding Ï-radial and Ï-axial molecular orbitals (MOs) which are mainly localized on nitrogen atoms. The orbital interactions have a hyperconjugation character. The bonding energy decomposition analysis showed that the cyclic interactions are about half covalent and half electrostatic. The covalent bonding is dominated by radial interactions. The aromaticity concept is not appropriate for description of bonding in cyclophosphazenes. The contribution of phosphorus d atomic orbitals to the concept of chemical bonding in phosphazenes is negligible, but the inclusion of d phosphorus functions in a basis set is appropriate for a correct quantitative description of electronic and geometric structure. Extended Hückel (EHT), ab initio and density functional (DFT) calculations provide the same qualitative picture of the bonding. The very flat B3LYP/6-311+G(3df)//B3LYP/6-31G(3df) potential energy surface (PES) with the low energy barrier (â¼1.6Â kJÂ molâ1) indicates the very fast and easy conformational motion of (F2PN)4. The global minimum on this PES is the S4 conformation.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Journal of Molecular Structure: THEOCHEM - Volume 820, Issues 1â3, 15 October 2007, Pages 148-158
Journal: Journal of Molecular Structure: THEOCHEM - Volume 820, Issues 1â3, 15 October 2007, Pages 148-158
نویسندگان
Libor KapiÄka, Pavel KubáÄek, Petr Holub,