Electron deficient bridges involving silylenes: A theoretical study

Ab initio and density functional studies show that silylenes can form complexes with BH3 and the resultant complexes possess 3c-2e bridges. The complexation energy for the formation of the these H-bridged structures is in the range of 18-46 kcal/mol. The characteristics of the electron deficient bridges depend on the substituents attached to the silylenes. With an increase in the pi-donating capacity of the substituents, the exothermicity of complex formation gets reduced but the kinetic stability of the H-bridged structures increase. The natural bond orbital analysis shows that all the H-bridged structures are associated with sigma(B-H)-->ppi(Si) second-order delocalization, which is responsible for the origin of the 3c-2e bonds. The complexation energies of the silylene-BH3 complexes have been shown to have a correlation to the singlet-triplet energy gaps of silylenes.