Phosphine-Enhanced Semi-Hydrogenation of Phenylacetylene by Cobalt Phosphide Nano-Urchins.

Autor: Ropp A; Sorbonne Université, CNRS, Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), 4 place Jussieu, 75005, Paris, France., André RF; Sorbonne Université, CNRS, Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), 4 place Jussieu, 75005, Paris, France., Carenco S; Sorbonne Université, CNRS, Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), 4 place Jussieu, 75005, Paris, France.
Jazyk: angličtina
Zdroj: ChemPlusChem [Chempluschem] 2023 Nov; Vol. 88 (11), pp. e202300469. Date of Electronic Publication: 2023 Oct 05.
DOI: 10.1002/cplu.202300469
Abstrakt: Transition metal phosphides are promising, selective, and air-stable nanocatalysts for hydrogenation reactions. However, they often require fairly high temperatures and H 2 pressures to provide quantitative conversions. This work reports the positive effect of phosphine additives on the activity of cobalt phosphide nano-urchins for the semi-hydrogenation of phenylacetylene. While the nanocatalyst's activity was low under mild conditions (7 bar of H 2 , 100 °C), the addition of a catalytic amount of phosphine remarkably increased the conversion, e. g., from 13 % to 98 % in the case of P n Bu 3 . The heterogeneous nature of the catalyst was confirmed by negative supernatant activity tests. The catalyst integrity was carefully verified by post-mortem analyses (TEM, XPS, and liquid 31 P NMR). A stereo-electronic map was proposed to rationalize the activity enhancement provided over a selection of nine phosphines: the strongest effect was observed for low to moderately hindered phosphines, associated with strong electron donor abilities. A threshold in phosphine stoichiometry was revealed for the enhancement of activity to occur, which was related to the ratio of phosphine to surface cobalt atoms.
(© 2023 The Authors. ChemPlusChem published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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