Calix[4]pyrrolato aluminates: the effect of Ligand Modification on the reactivity of square-planar aluminum anions
Structural constraint represents an attractive tool to modify p-block element properties without the need for unusual oxidation or valence states. The recently reported methyl-calix[4]pyrrolato aluminate established the effect of forcing a tetrahedral aluminum anion into a square-planar coordination...
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| Main Authors: | , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
2021
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| In: |
Chemistry - a European journal
Year: 2021, Volume: 27, Issue: 16, Pages: 5120-5124 |
| ISSN: | 1521-3765 |
| DOI: | 10.1002/chem.202005493 |
| Online Access: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1002/chem.202005493 Verlag, lizenzpflichtig, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.202005493 
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| Author Notes: | Fabian Ebner, Philipp Mainik, Lutz Greb |
| Summary: | Structural constraint represents an attractive tool to modify p-block element properties without the need for unusual oxidation or valence states. The recently reported methyl-calix[4]pyrrolato aluminate established the effect of forcing a tetrahedral aluminum anion into a square-planar coordination mode. However, the generality of this structural motif and any consequence of ligand modification remained open. Herein, a systematic ligand screening was launched, and the class of square-planar aluminum anions was extended by two derivatives that differ in the meso-substitution at the calix[4]pyrrolato ligand. Strikingly, this modification provoked opposing trends in the preference for a Lewis acidic binding mode with σ-donors versus the aluminum-ligand cooperative binding mode with carbonyls. Insights into the origin of these counterintuitive experimental observations were provided by computation and bond analysis. Importantly, this rationale might allow to exploit mode-selective binding for catalytic rate control. |
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| Item Description: | Gesehen am 20.04.2023 |
| Physical Description: | Online Resource |
| ISSN: | 1521-3765 |
| DOI: | 10.1002/chem.202005493 |