The mechanochemical reaction of LiBH₄ with MnCl₂ produces the neutral complex Mn(BH₄)₂. Thermal desorption studies show that the mechanochemical reaction of NaBH₄ with MnCl₂produces a different species, apparently Na₂Mn(BH₄)₄, that undergoes dehydrogenation of a much lower weight percent H at a ~20 °C higher temperature than the neutral Mn(BH₄)₂. Vibrational spectroscopy also reveals that a complex manganese borohydride(s) in addition to Mn(BH₄)₂ are formed from the mechanochemical reactions. Analysis of the vibrational spectra in conjunction with DFT calculations on a model Mn(BH₄)₄^2− complex suggest bidentate binding of the [BH₄]^− ligands to the Mn center in the anionic complex. The calculated highest frequencies of the B−H stretching modes (corresponding to the “freeâ€� B−H bonds) agree well with the experimental frequencies and support the presence of this structural feature.

LiSc(BH₄)₄ has been prepared by ball milling of LiBH₄ and ScCl₃. Vibrational spectroscopy indicates the presence of discrete Sc(BH₄)₄^− ions. DFT calculations of this isolated complex ion confirm that it is a stable complex, and the calculated vibrational spectra agree well with the experimental ones. The four BH₄^− groups are oriented with a tilted plane of three hydrogen atoms directed to the central Sc ion, resulting in a global 8 + 4 coordination. The crystal structure obtained by high-resolution synchrotron powder diffraction reveals a tetragonal unit cell with a = 6.076 Ã… and c = 12.034 Ã… (space group P-42c). The local structure of the Sc(BH₄)₄^− complex is refined as a distorted form of the theoretical structure. The Li ions are found to be disordered along the z axis.

IR and Raman data were obtained from α-, β-, and mixed (β,γ)-Ca(BH ₄) ₂ samples and from the deuterated β,γ phase mixture. The results obtained with α phase indicate that the DFT calculated values for the B−H stretching modes and the lattice vibrations are fairly close to the experimental values. The spectral behavior at temperatures around the transition to the β phase shows a continuous transition and suggests the presence of disorder caused by reorientational motions of the [BH ₄] ^− ion in the β phase. The data indicate that there are more deformation bands observed for the mixed (β,γ) samples than for the α phase which indicates structural variations between the β and the γ phases.