Mechanistic insight into alkali-metal mediation of styrene transfer hydrogenation : a DFT study

Byrne, Keelan M and Robertson, Stuart D and Mulvey, Robert E and Kraemer, Tobias (2024) Mechanistic insight into alkali-metal mediation of styrene transfer hydrogenation : a DFT study. ChemCatChem. ISSN 1867-3880 (https://doi.org/10.1002/cctc.202400655)

[thumbnail of Byrne-etal-ChemCatChem-2024-Mechanistic-insight-into-alkali-metal-mediation-of-styrene-transfer-hydrogenation] Text. Filename: Byrne-etal-ChemCatChem-2024-Mechanistic-insight-into-alkali-metal-mediation-of-styrene-transfer-hydrogenation.pdf
Accepted Author Manuscript
Restricted to Repository staff only until 1 January 2099.
Download (3MB) | Request a copy

Abstract

A computational mechanistic study was performed to investigate the transfer hydrogenation of styrene catalysed by a potassium tris‐hexamethyldisilazide magnesiate in the presence of 1,4‐cyclohexadiene. Exploiting cooperative effects between Mg and K centres present in this tris(amide) complex results in the selective formation of the desired product ethylbenzene. The calculations demonstrate the synergy of the metal centres within the bimetallic complex, since neither the monometallic potassium amide K(HMDS) nor the magnesium amide Mg(HMDS)2 on their own can efficiently execute this transformation under the experimental conditions. Several distinct mechanistic pathways have been explored, leading to the identification of the most plausible sequence in which both metal centres act in a synchronised manner.

  • Item type:Article
    ID code:89801
    Dates:
    Date
    Event
    18 June 2024
    Published
    18 June 2024
    Published Online
    16 June 2024
    Accepted
    8 April 2024
    Submitted
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:01 Jul 2024 15:28
    Last modified:16 Jul 2024 01:53
    URI:https://strathprints.strath.ac.uk/id/eprint/89801
CORE (COnnecting REpositories)