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. A tale of two disilenes: The addition of acetonitrile to tetramesityldisilene was examined in order to compare the structures of the molecular adducts with the structures of the acetonitrile adducts formed on the Si(100)‐2×1 surface and to provide further insight into the surface chemistry. The reactivity of propionitrile and phenylacetonitrile towards this disilene was also studied to investigate reactivity trends (see scheme).