Neutral and cationic phosphoramide adducts of silicon tetrachloride: synthesis and characterization of their solution and solid-state structures.

The solution and solid-state structures of hexamethylphosphoramide (HMPA) adducts of tetrachlorosilane (SiCl4) are discussed. In solution, the meridional and facial isomers of the hexa-coordinate cationic complex 3 HMPASiCl3 + Cl(-) (2) predominate at all HMPA concentrations, and are in equilibrium with the hexa-coordinate neutral trans- and cis-2 HMPASiCl4 complexes (1), as well as the penta-coordinate cationic cis-2 HMPASiCl3 + Cl(-) (3). Single crystal X-ray analyses are reported for the ionized mer-3 HMPASiCl3 + HCl2 (-) and the neutral trans-2 HMPASiCl4 complexes.