Elucidation of hydrogen-release mechanism from methylamine in the presence of borane, alane, diborane, dialane, and borane–alane

The mechanisms of hydrogen release from methylamine with or without borane, alane, diborane, dialane, and borane–alane are theoretically explored. Geometries of stationary points are optimised at the MP2/aug-cc-pVDZ level and energy profiles are refined at the CCSD(T)/aug-cc-pVTZ level based on the second-order Møller–Plesset (MP2) optimised geometries. H₂ elimination is impossible from the unimolecular CH₃NH₂ because of a high energy barrier. The results show that all catalysts can facilitate H₂ loss from CH₃NH₂. However, borane or alane has no real catalytic effect because the H₂ release is not preferred as compared with the B–N or Al–N bond cleavage once a corresponding adduct is formed. The diborane, dialane, and borane–alane will lead to a substantial reduction of energy barrier as a bifunctional catalyst. The similar and distinct points among various catalysts are compared. Hydrogen bond and six-membered ring formation are two crucial factors to decrease the energy barriers.