[Si(O2C6F4)2]14: Self‐Assembly of a Giant Perfluorinated Macrocyclic Host by Low‐Barrier Si−O Bond Metathesis. Issue 50 (2nd October 2020)

• Record Type: Journal Article
• Authors: Hartmann, Deborah; Greb, Lutz
• Is Part Of: Angewandte Chemie international edition. Volume 59:Issue 50(2020)
• Page Start: 22510
• Page End: 22513
• Publication Date: 2020-10-02
• Subjects: catecholates -- dynamic covalent chemistry -- host––guest systems -- macrocycles -- silicon–oxygen bonds; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202009942
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The dynamic covalent self‐assembly of 14 units of bis(perfluorocatecholato)silane leads to [Si(O2 C6 F4 )2 ]14 —the first giant perfluorinated macrocycle. The oligomerization process is monitored spectroscopically, and the macrocycle analyzed by single‐crystal X‐ray diffraction. The molecule forms a rigid cavity that can host two o ‐closo‐dodecacarboranes. Computations rationalize the consistent and reproducible formation of the 14mer and disclose a non‐catalyzed Si−O/ Si−O σ‐bond metathesis with an exceptionally low energetic barrier. For the first time, the most prevalent linker in our geosphere‐SiO4 ‐is disposed to construct a shape‐defined crystalline macromolecule. Abstract : The dynamic covalent self‐assembly of fourteen units of bis(perfluorocatecholato)silane delivers a giant perfluorinated macrocycle. The oligomerization process occurs by an unprecedented low‐barrier silicon–oxygen σ‐bond metathesis—revealing constitutional dynamics for one of the strongest bonds in our geosphere.