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Issue 35, 2020
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Reversible OH-bond activation and amphoterism by metal–ligand cooperativity of calix[4]pyrrolato aluminate

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Abstract

Most p-block metal amides irreversibly react with metal alkoxides when subjected to alcohols, making reversible transformations with OH-substrates a challenging task. Herein, we describe how the combination of a Lewis acidic square-planar-coordinated aluminum(III) center with metal–ligand cooperativity leverages unconventional reactivity toward protic substrates. Calix[4]pyrrolato aluminate performs OH-bond activation of primary, secondary, and tertiary aliphatic and aromatic alcohols, which can be fully reversed under reduced pressure. The products exhibit a new form of metal–ligand cooperative amphoterism and undergo counterintuitive substitution reactions of a polar covalent Al–O bond by a dative Al–N bond. A comprehensive mechanistic picture of all processes is buttressed by isolation of intermediates, spectroscopy, and computation. This study delineates how structural constraints can invert thermodynamics for seemingly simple addition reactions and invert common trends in bond energies.

Graphical abstract: Reversible OH-bond activation and amphoterism by metal–ligand cooperativity of calix[4]pyrrolato aluminate

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Supplementary files

Article information


Submitted
30 Jun 2020
Accepted
19 Aug 2020
First published
20 Aug 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020,11, 9611-9616
Article type
Edge Article

Reversible OH-bond activation and amphoterism by metal–ligand cooperativity of calix[4]pyrrolato aluminate

L. M. Sigmund and L. Greb, Chem. Sci., 2020, 11, 9611
DOI: 10.1039/D0SC03602A

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