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NONEMPIRICAL QUANTUM-CHEMICAL CALCULATION FOR NITRAMIDE, ITS CHLOROSUBSTITUTED AND METHYL-SUBSTITUTED DERIVATIVES .2. STRUCTURES AND ENERGIES OF TRANSITION-STATES FOR INTERNAL-ROTATION AND INVERSION OF THE AMINO GROUPстатья
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Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 18 июля 2013 г.
- Авторы: KHAIKIN LS, GRIKINA OE, VILKOV LV, BOGGS JE
- Журнал: Journal of Structural Chemistry
- Том: 34
- Номер: 1
- Год издания: 1993
- Издательство: Maik Nauka/Interperiodica Publishing
- Местоположение издательства: Russian Federation
- Первая страница: 9
- Последняя страница: 16
- DOI: 10.1007/BF00745395
- Аннотация: For five N-nitramines (H2NNO2, MeNHNO2, ClNHNO2, MeNClNO2, Me2NNO2) using the program GAUSSIAN-90 we have carried out quantum chemical calculations by the restricted Hartree-Fock method, taking into account electron correlation by second-order Moller-Plesset perturbation theory in a standard 6-31G* basis. In this paper, we consider the transition states for inversion of the amine nitrogen atom and rotation about the NN bond. We have obtained data on the changes in the geometric parameters during inversion and rotation. The changes in the NN bond length are especially significant: they increase by 0.06-0.08 angstrom in the transition states for internal rotation compared with the equilibrium forms. We have calculated the barriers to inversion and internal rotation, the height of which strongly depends on the electronegativity of the substituents on the amine nitrogen atom. Estimates of the barriers to inversion lie within the range 0.4-60 kcal/mole while estimates of the barriers to rotation lie within the range 6-13 kcal/mole, which are 1.5-2 times lower than in amides and N-nitrosoamines.
- Добавил в систему: Хайкин Леонид Соломонович