Issue 1, 2017

Tailored oxido-vanadium(V) cage complexes for selective sulfoxidation in confined spaces

Abstract

Five sets of oxido-vanadium(V) complexes, which include both cages and open structures, were prepared and tested in the catalytic oxidation of sulfides. It was found that the hemicryptophane complexes, which are simultaneously comprised of cyclotriveratrylene (CTV), binaphthol and oxido-vanadium(V) moieties, are the most efficient supramolecular catalysts. The specific shape of the confined hydrophobic space above the metal center leads to a strong improvement in the yield, selectivity and rate of the reaction, compared to the other catalysts investigated herein. A remarkable turnover number (TON) of 10 000 was obtained, which can be attributed to both the high reactivity and stability of the catalyst. Similarly to enzymes, the kinetic analysis shows that the mechanism of oxidation with the supramolecular catalysts obeys the Michaelis–Menten model, in which initial rate saturation occurs upon an increase in substrate concentration. This enzyme-like behavior is also supported by the competitive inhibition and substrate size-selectivity observed, which underline the crucial role played by the cavity.

Graphical abstract: Tailored oxido-vanadium(V) cage complexes for selective sulfoxidation in confined spaces

Supplementary files

Article information

Article type
Edge Article
Submitted
11 Jul 2016
Accepted
04 Sep 2016
First published
05 Sep 2016
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., 2017,8, 789-794

Tailored oxido-vanadium(V) cage complexes for selective sulfoxidation in confined spaces

D. Zhang, K. Jamieson, L. Guy, G. Gao, J. Dutasta and A. Martinez, Chem. Sci., 2017, 8, 789 DOI: 10.1039/C6SC03045A

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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