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Abstract

Density functional theory (DFT) has been used to investigate the mechanism of the experimentally efficient hydroalkylation of styrene with acetylacetone in the presence of a bismuth catalyst. It is shown that the mechanism is fundamentally different to that of the analogous gold-catalysed reaction, even though it leads to the same product. Whereas gold prefers to coordinate to the π-bond of the enol isomer of acetylacetone, bismuth coordinates to the two oxygens to form a chelated complex. Furthermore, the overall reaction with bismuth via the enol isomer of acetylacetone occurs with a much lower activation energy compared to the ketone isomer. In addition, several bismuth catalysts were considered and two of these were shown to have no activity. All of these results have been rationalised in terms of the strength of binding of the metal centres to the acetylacetone. The stronger the binding, the greater the acidity of a proton on acetylacetone, and thus the lower the activation energy for the protonation of styrene, which turns out to be the rate-determining step in the overall reaction. In this way, good agreement is obtained with all the experimental data.

Item Type:	Article
Authors/Creators:	Jalali, M and Shiri, F and Bissember, AC and Yates, BF and Ariafard, A
Keywords:	density functional theory (DFT), bismuth(III) catalysis, reaction mechanism, hydroalkylation, styrene
Journal or Publication Title:	Molecular Physics
Publisher:	Taylor & Francis Ltd
ISSN:	0026-8976
DOI / ID Number:	10.1080/00268976.2022.2093798
Copyright Information:	© 2022 Informa UK Limited, trading as Taylor & Francis Group
Related URLs:	UTAS Profile: Bissember, AC Google Scholar: Yates, BF UTAS Profile: Yates, BF Google Scholar: Ariafard, A UTAS Profile: Ariafard, A
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