An Improved Synthesis of PN-adamantanoid Cages P4 (NR)6 and a Mechanistic Study of their Fourfold Oxidation.

Phosphorus-nitrogen (PN) adamantanoid cages are valuable precursors for materials chemistry, but their syntheses are based on harsh methods that sometimes require access to restricted reagents. We report a new and scalable synthesis of PN adamantanoid compounds by chlorosilane elimination between bis-silylated amines and phosphorus trichloride. We further study the mechanism of the recently-reported four-fold oxidation of such cages with Me3 SiN3 to yield tetravalent tetrahedral connectors for materials chemistry. Reaction monitoring and kinetic modelling revealed the key rate-limiting step, but attempts to accelerate this using Lewis acid additives were unsuccessful. Nevertheless, a new four-fold oxidized PN-adamantanoid cage has been prepared and structurally characterized.