Title: Molecular mechanism for H-2 release from BH3NH3, including the catalytic role of the lewis acid BH3
Authors: Nguyen, Minh Tho ×
Nguyen, Vinh Son
Matus, Myrna H
Gopakumar, G
Dixon, David A #
Issue Date: Feb-2007
Series Title: Journal of Physical Chemistry A vol:111 issue:4 pages:679-690
Conference: date:Univ Alabama, Dept Chem, Tuscaloosa, AL 35487 USA; Univ Louvain, Dept Chem, B-3001 Louvain, Belgium
Abstract: Electronic structure calculations using various methods, up to the coupled-cluster CCSD(T) level, in conjunction with the aug-cc-pVnZ basis sets with n = D, T, and Q, extrapolated to the complete basis set limit, show that the borane molecule (BH3) can act as an efficient bifunctional acid-base catalyst in the H-2 elimination reactions of XHnYHn systems (X, Y = C, B, N). Such a catalyst is needed as the generation of H-2 from isoelectronic ethane and borane amine compounds proceeds with an energy barrier much higher than that of the X-Y bond energy. The asymptotic energy barrier for H-2 release is reduced from 36.4 kcal/mol in BH3NH3 to 6.0 kcal/mol with the presence of BH3 relative to the molecular asymptote. The NH3 molecule can also participate in a similar catalytic process but induces a smaller reduction of the energy barrier. The kinetics of these processes was analyzed by both transition-state and RRKM theory. The catalytic effect of BH3 has also been probed by an analysis of the electronic densities of the transition structures using the atom-in-molecule (AIM) and electron localization function (ELF) approaches.
ISSN: 1089-5639
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Quantum Chemistry and Physical Chemistry Section
× corresponding author
# (joint) last author

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