title: Initial gas phase reactions between Al(CH3)3/AlH3 and ammonia: theoretical study.
abstract: 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)3NH3 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 hydrogen-substituted species may serve as an upper estimate in studying the reactivity of methyl-substituted analogues in more complex systems.
authors.affiliation: Inorganic Chemistry Group, Institute of Chemistry, St. Petersburg State University , University Pr. 26, Old Peterhof, St. Petersburg, 198504, Russia.
authors.forename: Anna S
authors.initials: AS
authors.lastname: Lisovenko
authors.forename: Keiji
authors.initials: K
authors.lastname: Morokuma
authors.forename: Alexey Y
authors.initials: AY
authors.lastname: Timoshkin