Structure and bonding of KSiH3 and its 18-crown-6 derivatives: unusual ambidentate behavior of the SiH3(-) anion

Density functional theory (DFT) calculations of [K(18-crown-6)SiH(3)] (1) and KSiH(3) (2) have shown that both the classical tet and non-classical inv coordination modes of the [SiH(3)](-) anion to the K(+) ion are energetically accessible. Single-crystal X-ray structures of the tet and inv derivatives [K(18-crown-6)SiH(3)·THF] (1a) and [K(18-crown-6)SiH(3)·HSiPh(3)] (1b) confirm this conclusion, showing that small changes in the coordination sphere of the metal are sufficient to alter the orientation of the anion. A topological analysis of the calculated electron densities for 1 and 2 reveals that the K···Si interaction in the tet conformer of 2 possesses a significant amount of covalent character. In contrast, the inv form of 2 displays primarily electrostatic character for the K···Si and K···H interactions. Incorporation of the 18-crown-6 ligand in 1 reduces the polarizing power of the K(+) cation, hardening the cation-anion interaction in both conformers. The experimental structures of 1a and 1b bear out these conclusions, with the strongly bound tetrahydrofuran (THF) ligand softening the K(+) ion in 1a and favoring the tet conformer, while the weakly interacting HSiPh(3) ligand in 1b has minimal effect on the K(+) center, resulting in an inv orientation.