The dehydrogenations of silanes SiH4 and CH3SiH3 in the presence of borane and alane were investigated using density functional (B3LYP) and coupled-cluster (CCSD(T)/aug-cc-pVnZ) theories. The calculated results showed that the hydrogen release reactions are more favorable in presence of BH3. Our theoretical analyses have further revealed that the addition of an extra BH3 can lead to several low energy barrier pathways. This observation is important to understand the catalytic role of BH3 in such reactions (depending on its release mechanism). Overall, silane and its alkyl derivatives can be used as effective starting materials for H-2 production. (C) 2014 Elsevier B.V. All rights reserved.