(PNSiMe <sub>3</sub> ) <sub>4</sub> (NMe) <sub>6</sub> : A Robust Tetravalent Phosphaza‐adamantane Scaffold for Molecular and Macromolecular Construction**
Joseph Bedard, Nicholas J. Roberts, Mohsen Shayan, Karlee L. Bamford, Ulrike Werner‐Zwanziger, Katherine M. Marczenko, Saurabh S. Chitnis
Abstract
Abstract 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 ).