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

Abstract

AbstractPhosphorus‐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 Me3SiN3 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.