Issue 42, 2023

Broadening the catalytic region from the cavity to windows by M6L12 nanospheres in cyclizations

Abstract

Supramolecular cages have received tremendous attention as they can contain catalysts that exhibit confinement effects in the cavity, leading to excellent performances. Herein, we report an example wherein the catalytic region is extended from the cage cavity to the windows, and investigate its confinement effect by utilizing the Pd6LAu12 cage that contains rigidly fixed and isolated gold complexes at the windows. Pd6LAu12 exhibit three features of particular interest while assessing their properties in gold-catalyzed cyclization reactions. First, the catalysts experience a cage effect as they display higher reactivity and selectivity compared to the monomeric analogue, as a result of substrate pre-organization at the windows. Second, the metal complexes are physically separated by the cage structure, preventing the formation of less active dinuclear gold complexes making it more stable under hydrous conditions. Third, the cage windows present the characteristics of enzymatic catalysis via Michaelis–Menten-type mechanism analysis. This contribution presents an alternative way to engineer supramolecular catalysts through extending the catalytic region.

Graphical abstract: Broadening the catalytic region from the cavity to windows by M6L12 nanospheres in cyclizations

Supplementary files

Article information

Article type
Edge Article
Submitted
13 Чер 2023
Accepted
24 Вер 2023
First published
26 Вер 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2023,14, 11699-11707

Broadening the catalytic region from the cavity to windows by M6L12 nanospheres in cyclizations

M. Xu, B. Sun, D. A. Poole, E. O. Bobylev, X. Jing, J. Wu, C. He, C. Duan and J. N. H. Reek, Chem. Sci., 2023, 14, 11699 DOI: 10.1039/D3SC02998K

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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