Metal-ligand cooperativity of the calix(4)pyrrolato aluminate: triggerable C-C bond formation and rate control in catalysis
Metal-ligand cooperativity (MLC) had a remarkable impact on transition metal chemistry and catalysis. By use of the calix[4]pyrrolato aluminate, [1]−, which features a square-planar AlIII, we transfer this concept into the p-block and fully elucidate its mechanisms by experiment and theory. Compleme...
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| Main Authors: | , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
September 21, 2020
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| In: |
Angewandte Chemie
Year: 2020, Volume: 132, Issue: 39, Pages: 17266-17272 |
| ISSN: | 1521-3757 |
| DOI: | 10.1002/ange.202007717 |
| Online Access: | Verlag, kostenfrei, Volltext: https://doi.org/10.1002/ange.202007717 Verlag, kostenfrei, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/ange.202007717 
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| Author Notes: | Fabian Ebner, Lukas Maximilian Sigmund und Lutz Greb |
| Summary: | Metal-ligand cooperativity (MLC) had a remarkable impact on transition metal chemistry and catalysis. By use of the calix[4]pyrrolato aluminate, [1]−, which features a square-planar AlIII, we transfer this concept into the p-block and fully elucidate its mechanisms by experiment and theory. Complementary to transition metal-based MLC (aromatization upon substrate binding), substrate binding in [1]− occurs by dearomatization of the ligand. The aluminate trapps carbonyls by the formation of C−C and Al−O bonds, but the products maintain full reversibility and outstanding dynamic exchange rates. Remarkably, the C−C bonds can be formed or cleaved by the addition or removal of lithium cations, permitting unprecedented control over the system's constitutional state. Moreover, the metal-ligand cooperative substrate interaction allows to twist the kinetics of catalytic hydroboration reactions in a unique sense. Ultimately, this work describes the evolution of an anti-van't Hoff/Le Bel species from their being as a structural curiosity to their application as a reagent and catalyst. |
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| Item Description: | Im Titel steht die 4 in eckiger Klammer First published: 23 June 2020 Gesehen am 02.11.2021 |
| Physical Description: | Online Resource |
| ISSN: | 1521-3757 |
| DOI: | 10.1002/ange.202007717 |