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Trimeric cluster of lithium amidoborane—the smallest unit for the modeling of hydrogen release mechanism
Author(s) -
Pomogaeva Anna V.,
Morokuma Keiji,
Timoshkin Alexey Y.
Publication year - 2016
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.24316
Subject(s) - moiety , chemistry , dehydrogenation , trimer , cluster (spacecraft) , molecule , lithium (medication) , hydrogen , hydrogen atom , crystallography , reaction mechanism , lithium atom , stereochemistry , computational chemistry , group (periodic table) , catalysis , ion , organic chemistry , dimer , medicine , ionization , computer science , programming language , endocrinology
A detailed first‐principle DFT M06/6‐311++G(d.p) study of dehydrogenation mechanism of trimeric cluster of lithium amidoborane is presented. The first step of the reaction is association of two LiNH 2 BH 3 molecules in the cluster. The dominant feature of the subsequent reaction pathway is activation of H atom of BH 3 group by three Li atoms with formation of unique Li 3 H moiety. This Li 3 H moiety is destroyed prior to dehydrogenation in favor of formation of a triangular Li 2 H moiety, which interacts with protic H atom of NH 2 group. As a result of this interaction, Li 2 H 2 moiety is produced. It features N − H + H − group suited near the middle plane between two Li + in the transition state that leads to H 2 release. The transition states of association and hydrogen release steps are similar in energy. It is concluded that the trimer, (LiNH 2 BH 3 ) 3 , is the smallest cluster that captures the essence of the hydrogen release reaction. © 2016 Wiley Periodicals, Inc.