Unravelling the Metastable Nature of the Single Site Tungsten Hydride Metathesis Catalyst Supported on γ‑Alumina from First Principles

We explore the structure and formation mechanism of the surface tungsten hydride complex supported on alumina, which is a catalyst for alkane and alkene metathesis and cross-metathesis. We show that the kinetics for the formation reaction of the hydride from the grafted alkylidyne–alkyl W complex st...

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Bibliographic Details
Published in:Journal of physical chemistry. C 2019-01, Vol.123 (2), p.1226-1234
Main Authors: Joubert, Jérôme, Delbecq, Françoise, Sautet, Philippe
Format: Article
Language:English
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Summary:We explore the structure and formation mechanism of the surface tungsten hydride complex supported on alumina, which is a catalyst for alkane and alkene metathesis and cross-metathesis. We show that the kinetics for the formation reaction of the hydride from the grafted alkylidyne–alkyl W complex strongly favors the creation of a metastable WVI trihydride, which is less coordinated by the alumina surface than the most stable isomer. The reaction network for the hydride formation involves hydrogenation of the WC or WC bond, hydrogenolysis of W–C bonds, and a second grafting step. The creation of metastable surface complexes is proposed to be a key path for the design of active and selective catalysts.
ISSN:1932-7447
1932-7455
DOI:10.1021/acs.jpcc.8b09876