Nucleophilic Substitution Reactions in the [B3H8]− Anion in the Presence of Lewis Acids

As a result of our study on the interaction between the octahydrotriborate anion with nucleophiles (Nu = THF, Ph₃P, Ph₂P-(CH₂)₂-PPh₂ (dppe), Ph₃As, Et₃N, PhNH₂, C₅H₅N, CH₃CN, Ph₂CHCN)) in the presence of a wide range of Lewis acids (Ti(IV), Hf(IV), Zr(IV), Al, Cu(I), Zn, Mn(II), Co(II) halides and iodine), a number of substituted derivatives of the octahydrotriborate anion [B₃H₇Nu] are obtained. It is found that the use of TiCl₄, AlCl₃, ZrCl₄, HfCl₄, CuCl and iodine leads to the highest product yields. In this case, it is most likely that the reaction proceeds through the formation of an intermediate [B₃H₇-HMXn_x], which was detected by NMR spectroscopy. The structures of [Ph₃P·B₃H₇] and [PhNH₂·B₃H₇] were determined by X-ray diffraction.