Structural and Vibrational Properties of Silyl (SiH3-) Anions in KSiH3 and RbSiH3: New Insight into Si-H Interactions

Journal article, 2015

The alkali metal silyl hydrides ASiH(3) (A = K, Rb) and their deuteride analogues were prepared from the Zintl phases ASi. The crystal structures of ASiH(3) consist of metal cations and pyramidal SiH3 ions. At room temperature SiH3 moieties are randomly oriented (alpha modifications). At temperatures below 200 K ASiH(3) exist as ordered low-temperature (beta) modifications. Structural and vibrational properties of SiH3- in ASiH(3) were characterized by a combination of neutron total scattering experiments, infrared and Raman spectroscopy, as well as density functional theory calculations. In disordered alpha-ASiH(3) SiH3 ions relate closely to freely rotating moieties with C(3)v symmetry (Si-H bond length = 1.52 angstrom; HSiH angle 92.2 degrees). Observed stretches and bends are at 1909/1903 cm(-1) (nu(1), A(1)), 1883/1872 cm(-1) (nu(3), E), 988/986 cm(-1) (nu(4), E), and 897/894 cm(-1) (nu(2), A(1)) for A = K/Rb. In ordered beta-ASiH(3) silyl anions are slightly distorted with respect to their ideal C-3v symmetry. Compared to a-ASiH(3) the molar volume is by about 15% smaller and the SiH stretching force constant is reduced by 4%. These peculiarities are attributed to reorientational dynamics of SiH3 anions in a-ASiH(3). SiH stretching force constants for SiH3 moieties in various environments fall in a range from 1.9 to 2.05 N cm(-1). These values are considerably smaller compared to silane, SiH4 (2.77 N cm(-1)). The reason for the drastic reduction of bond strength in SiH3- remains to be explored.