Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
Initial Gas Phase Reactions between Al(CH3)(3)/AIH(3) and Ammonia: Theoretical Study. / Lisovenko, A. S.; Morokuma, K.; Timoshkin, A. Y.
в: Journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment & general theory, Том 119, № 4, 2015, стр. 744-751.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Initial Gas Phase Reactions between Al(CH3)(3)/AIH(3) and Ammonia: Theoretical Study
AU - Lisovenko, A. S.
AU - Morokuma, K.
AU - Timoshkin, A. Y
PY - 2015
Y1 - 2015
N2 - Mechanisms of initial stages of gas phase reactions between trimethylaluminum and ammonia have been explored by DFT studies. Subsequent substitution of CH3 groups in AlMe3 by amido groups and substitution of hydrogen atoms in ammonia by AlMe2 groups have been considered. Structures of Al(CH3)(x)(NH2)(3-x), NHx(Al(CH3)(2))(3-x) (x = 0-3) and related donor-acceptor complexes, dimerization products, and reaction pathways for the methane elimination have been obtained. The transition state for the first methane elimination from Al(CH3)(3)NH3 adduct is the highest point on the reaction pathway; subsequent processes are exothermic and do not require additional activation energy. In excess ammonia, subsequent methane elimination reactions may lead to formation of [Al(NH2)(3)](2), while in excess trimethylaluminum, formation of N(AlMe2)(3) is feasible. Formation of [AlMe2NH2](2) dimer is very favorable thermodynamically. Studies on model reactions between AlH3 and NH3 indicate that reaction barriers obtained for hydr
AB - Mechanisms of initial stages of gas phase reactions between trimethylaluminum and ammonia have been explored by DFT studies. Subsequent substitution of CH3 groups in AlMe3 by amido groups and substitution of hydrogen atoms in ammonia by AlMe2 groups have been considered. Structures of Al(CH3)(x)(NH2)(3-x), NHx(Al(CH3)(2))(3-x) (x = 0-3) and related donor-acceptor complexes, dimerization products, and reaction pathways for the methane elimination have been obtained. The transition state for the first methane elimination from Al(CH3)(3)NH3 adduct is the highest point on the reaction pathway; subsequent processes are exothermic and do not require additional activation energy. In excess ammonia, subsequent methane elimination reactions may lead to formation of [Al(NH2)(3)](2), while in excess trimethylaluminum, formation of N(AlMe2)(3) is feasible. Formation of [AlMe2NH2](2) dimer is very favorable thermodynamically. Studies on model reactions between AlH3 and NH3 indicate that reaction barriers obtained for hydr
U2 - 10.1021/jp507713b
DO - 10.1021/jp507713b
M3 - Article
VL - 119
SP - 744
EP - 751
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
SN - 1520-6106
IS - 4
ER -
ID: 4014055