The Addition of Nitriles to Tetramesityldisilene: A Comparison of the Reactivity between Surface and Molecular Disilenes

The addition of acetonitrile, propionitrile, and phenylacetonitrile to tetramesityldisilene (Mes₂Si?SiMes₂) was examined. In general, 1,2,3‐azadisiletines and the tautomeric enamines were formed, although a ketenimine was formed as the major product in the addition of phenylacetonitrile to the disilene. In the presence of LiCl, the mode of addition changed for both acetonitrile and propionitrile: insertion into the α‐CH bond of acetonitrile and/or formation of the formal HCN adduct was observed. Preliminary investigations of the reactivity of the nitrile adducts are also reported. A comparison between the reactivity of nitriles with Mes₂Si?SiMes₂ and the Si(100)‐2×1 surface was made both in terms of the types of adducts formed and their reactivity. Some insights into the surface chemistry are offered.