Nucleophilic Substitution Reactions in the [B(3)H(8)](−) Anion in the Presence of Lewis Acids

As a result of our study on the interaction between the octahydrotriborate anion with nucleophiles (Nu = THF, Ph(3)P, Ph(2)P-(CH(2))(2)-PPh(2) (dppe), Ph(3)As, Et(3)N, PhNH(2), C(5)H(5)N, CH(3)CN, Ph(2)CHCN)) 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 [B(3)H(7)Nu] are obtained. It is found that the use of TiCl(4), AlCl(3), ZrCl(4), HfCl(4), 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 [B(3)H(7)-HMXn(x)], which was detected by NMR spectroscopy. The structures of [Ph(3)P·B(3)H(7)] and [PhNH(2)·B(3)H(7)] were determined by X-ray diffraction.