Shaping Antiaromatic π‐Systems by Metalation: Synthesis of a Bowl‐Shaped Antiaromatic Palladium Norcorrole. Issue 39 (16th August 2017)

• Record Type: Journal Article
• Authors: Yonezawa, Tsubasa; Shafie, Siham A.; Hiroto, Satoru; Shinokubo, Hiroshi
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 39(2017)
• Page Start: 11822
• Page End: 11825
• Publication Date: 2017-08-16
• Subjects: aromaticity -- bowl-shaped molecules -- C-C coupling -- porphyrinoids -- strained molecules; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201706134
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The synthesis of a bowl‐shaped antiaromatic molecule was achieved through the deformation of a planar antiaromatic porphyrinic π‐conjugation system by insertion of palladium into the small cavity of a metal‐free norcorrole. The bowl‐to‐bowl inversion dynamics of the antiaromatic Pd‐coordinated norcorrole was determined by variable‐temperature 1 H NMR spectroscopy. The metal‐free norcorrole was prepared from acid‐induced demetalation of a copper norcorrole, which was obtained from the intramolecular coupling of a bis(diiododipyrrin) copper complex with copper thiophenecarboxylate. Abstract : A bowl‐shaped antiaromatic molecule was synthesized by deformation of a planar antiaromatic π‐conjugation system upon insertion of palladium into the small cavity of a metal‐free norcorrole. The latter was prepared through demetalation of a copper norcorrole obtained from the intramolecular coupling of a bis(diiododipyrrin) copper complex with copper thiophenecarboxylate.