(PNSiMe3)4(NMe)6: A Robust Tetravalent Phosphaza‐adamantane Scaffold for Molecular and Macromolecular Construction. Issue 25 (25th April 2022)

• Record Type: Journal Article
• Authors: Bedard, Joseph; Roberts, Nicholas J.; Shayan, Mohsen; Bamford, Karlee L.; Werner‐Zwanziger, Ulrike; Marczenko, Katherine M.; Chitnis, Saurabh S.
• Is Part Of: Angewandte Chemie international edition. Volume 61:Issue 25(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-04-25
• Subjects: Cages -- Inorganic Materials -- Molecular Connectors -- Phosphorus -- Polyphosphazenes; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202204851
• Languages: English
• ISSNs: 1433-7851

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, (PNSiMe3 )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 ). Abstract : The synthesis of a new air‐stable and thermally robust tetrahedral tetravalent inorganic cage, (PNSiMe3 )4 (NMe)6 has been achieved. This cage allows four‐fold functionalization reactions on its periphery to give unprecedented molecular and macromolecular constructs. This utility is shown by the synthesis of a tetrakis(bis(phosphine)iminium) ion and the first all P/N polyphazene network material.