Hydrosilyation Of Co2 Using A Silatrane Hydride: Structural Characterization Of A Silyl Formate Compound

The silatrane hydride compound, [N(CH2CH2O)(3)]SiH, reacts with CO2 in the presence of the [tris(2-pyridylthio)-methylizinc hydride complex, [Tptm]ZnH, to afford the silyl formate and methoxide derivatives, [N(CH2CH2O)(3)]SiO2CH and [N(CH2CH2O)(3)]SiOCH3. The molecular structure of [N(CH2CH2O)(3)]SiO2CH has been determined by X-ray diffraction, thereby demonstrating that the formate ligand adopts a distal conformation in which the uncoordinated oxygen atom resides with a trans-like disposition relative to silicon. Density functional theory calculations indicate that the atrane motif of [N(CH2CH2O)(3)]SiO2CH is flexible, such that the energy of the molecule changes relatively little as the Si center dot center dot center dot N distance varies over the range 2.0-3.0 angstrom.