Palladium Complexes of Corroles and Sapphyrins

• Published in: Chemistry : a European journal Vol. 26; no. 43; pp. 9481 - 9485
• Main Authors: Chen, Qiu‐Cheng, Fridman, Natalia, Diskin‐Posner, Yael, Gross, Zeev
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 03.08.2020; Wiley Subscription Services, Inc
• Subjects: Anions; Chemistry; Chemistry, Multidisciplinary; corroles; Crystallography; Ligands; Magnetic resonance spectroscopy; NMR; NMR spectroscopy; Nuclear magnetic resonance; Palladium; Physical Sciences; porphyrinoids; porphyrins; Pyridinium; sapphyrins; Science & Technology; Stereoisomerism; Stereoisomers; porphyrinoids; sapphyrins; DNA; palladium; PORPHYRIN; CATALYST; corroles; porphyrins
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202002682

Palladium complexes of corrole and sapphyrin were prepared in high yield and fully characterized. The corrole provides a tetradentate/trianionic square planar coordination sphere for PdII, charge balanced by pyridinium. Both one and two PdII ions may be accommodated by the pentapyrrolic skeleton of the sapphyrin, and in each case the macrocycle acts as bidentate/monoanionic ligand and the inner‐sphere square planar geometry is completed by allyl anions coordinated in an η3 fashion. NMR spectroscopy and X‐ray crystallography data analyses uncovered the presence of interesting stereoisomers due to the flexibility of the ally ligands and also the pyrrole ring(s) that is/are not involved in metal binding. Palladium insertion into the most prominent contracted and extended porphyrin analogs uncovered very different coordination modes for corroles and sapphyrin, as well as intriguing conformer isomerism for both the mono‐ and the bis‐palladium(II) complexes of the latter, which are stabilized by η3‐allyl groups (see scheme).