The gas-phase structure and some reactions of the bulky primary silane (Me3Si)3CSiH3 and the solid-state structure of the bulky dialkyl disilane [(Me3Si)3CSiH2]2Electronic supplementary information (ESI) available: Description of the model parameters for (Me3Si)3CSiH3. Tables: geometric parameters (distances in Å, angles in °) for both molecules in the solid-state structure of [(Me3Si)3CSiH2]2; calculated coordinates for (Me3Si)3CSiH3 at the MP2/6-31(d) level; interatomic distances (ra/Å), exper

The molecular structure of the bulky primary silane, (Me 3 Si) 3 CSiH 3 , in the gas phase has been determined by electron diffraction. Photolysis of (Me 3 Si) 3 CSiH 3 affords a convenient route to the bulky dialkyl disilane, [(Me 3 Si) 3 CSiH 2 ] 2 , which is the first 1,2-dialkyldisilane to be structurally characterised by single-crystal X-ray diffraction. The disilane has an unusually large Si-Si-C angle of 120.05(9)°. The molecular structures of (Me 3 Si) 3 CSiH 3 and [(Me 3 Si) 3 CSiH 2 ] 2 are reported; photolysis of the former provides a convenient route to the latter.