The viability of the hydroboration reaction of borane with disilenes, the heavier molecular analogue of alkenes, has theoretically been predicted using density functional theory calculations. The as-formed disilboranes could further be chemically functionalized given the well-known abundance of organoborane chemistry of alkenes. Interestingly, it was found that the detailed reaction mechanism of disilenes with borane is different from that of alkenes. Our theoretical results also present an instructive hint to experiments that, regarding disilenes protected by bulky-group ligands, disilenes with high planarity around the Si=Si double bond should be preferred to test if the hydroboration reaction of disilenes with boron-containing reagents can be realized. Furthermore, our results strongly reinforce the concept that similar and quite intriguing chemistry can lie in the material featuring analogous bonding motif. (c) 2006 Elsevier B.V. All rights reserved.