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

Content Provider	Royal Society of Chemistry (RSC)
Author	Martinez, Alexandre Zhang, Dawei Guy, Laure Gao, Guohua Dutasta, Jean-Pierre Jamieson, Kelsey
Copyright Year	2017
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.
Starting Page	789
Ending Page	794
Page Count	6
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	8
Issue Number	1
Journal	Chemical Science
DOI	10.1039/c6sc03045a
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Subscribed
Subject Keyword	CTV Television Network Cyclotriveratrylene Michaelis Hydrophobe Turnover number Competitive inhibition
Content Type	Text
Resource Type	Article
Subject	Chemistry

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