(PNSiMe 3 ) 4 (NMe) 6 : A Robust Tetravalent Phosphaza-adamantane Scaffold for Molecular and Macromolecular Construction.

Tetraarylmethanes and adamantanes are important rigid covalent connectors that play a four-way scaffolding role in molecular and materials chemistry. We report the synthesis of a new tetravalent phosphaza-adamantane cage, (PNSiMe 3 ) 4 (NMe) 6 (2), that shows high thermal, air, and redox stability due to its geometry. It nevertheless participates in covalent four-fold functionalization reactions along its periphery. The combination of a robust core and reactive corona makes 2 a convenient inorganic scaffold upon which tetrahedral molecular and macromolecular chemistry can be constructed. This potential is demonstrated by the synthesis of a tetrakis(bis(phosphine)iminium) ion (in compound 3) and the first all P/N poly(phosphazene) network (5).