Calix(4)pyrroles as ligands: recent progress with a focus on the emerging p-block element chemistry
Calix[4]pyrroles are readily synthesized in one step from pyrroles and ketones. For several decades, these macrocycles have been exploited as powerful anion receptors or ligands for transition and rare-earth metals. In contrast, calix[4]pyrrolates as ligands for p-block elements were established onl...
Gespeichert in:
| Hauptverfasser: | , , |
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| Dokumenttyp: | Article (Journal) |
| Sprache: | Englisch |
| Veröffentlicht: |
13 October 2021
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| In: |
Chemical communications
Year: 2021, Jahrgang: 57, Heft: 89, Pages: 11751-11763 |
| ISSN: | 1364-548X |
| DOI: | 10.1039/D1CC05120B |
| Online-Zugang: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1039/D1CC05120B Verlag, lizenzpflichtig, Volltext: https://pubs.rsc.org/en/content/articlelanding/2021/cc/d1cc05120b 
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| Verfasserangaben: | Heiko Ruppert, Lukas M. Sigmund and Lutz Greb |
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| 520 | |a Calix[4]pyrroles are readily synthesized in one step from pyrroles and ketones. For several decades, these macrocycles have been exploited as powerful anion receptors or ligands for transition and rare-earth metals. In contrast, calix[4]pyrrolates as ligands for p-block elements were established only in 2018. The present feature article reviews these developments, together with the recent progress on s-, d-, and f-block element complexes of the calix[4]pyrroles. Particular focus is given on the calix[4]pyrrolato aluminate and the corresponding silane, both featuring square planar-coordinated p-block elements in their highest oxidation states. These unique “anti-van’t-Hoff-Le-Bel” structures introduce valuable characteristics into main-group element chemistry, such as agostic interactions or ligand-to-metal charge transfer absorptions. The most vital reactivities are highlighted, which rely on properties ranging from amphoterism, redox-activity, and a small HOMO-LUMO gap up to the ability to provide a platform for additional external stimuli. Overall, these developments underscore the beneficial impact of structural constraint of p-block elements and element-ligand cooperativity to enhance the functionality of the most abundant elements in their native oxidation states. | ||
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