Dialumenes – aryl vs. silyl stabilisation for small molecule activation and catalysis

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Weetman, Catherine and Porzelt, Amelie and Bag, Prasenjit and Hanusch, Franziska and Inoue, Shigeyoshi (2020) Dialumenes – aryl vs. silyl stabilisation for small molecule activation and catalysis. Chemical Science, 11 (18). pp. 4817-4827. ISSN 2041-6539 (https://doi.org/10.1039/D0SC01561J)

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Abstract

Main group multiple bonds have proven their ability to act as transition metal mimics in the last few decades. However, catalytic application of these species is still in its infancy. Herein we report the second neutral NHC-stabilised dialumene species by use of a supporting aryl ligand (3). Different to the trans-planar silyl-substituted dialumene (3Si), compound 3 features a trans-bent and twisted geometry. The differences between the two dialumenes are explored computationally (using B3LYP-D3/6-311G(d)) as well as experimentally. A high influence of the ligand's steric demand on the structural motif is revealed, giving rise to enhanced reactivity of 3 enabled by a higher flexibility in addition to different polarisation of the aluminium centres. As such, facile activation of dihydrogen is now achievable. The influence of ligand choice is further implicated in two different catalytic reactions; not only is the aryl-stabilised dialumene more catalytically active but the resulting product distributions also differ, thus indicating the likelihood of alternate mechanisms simply through a change of supporting ligand.

ORCID iDs

Weetman, Catherine ORCID logoORCID: https://orcid.org/0000-0001-5643-9256, Porzelt, Amelie, Bag, Prasenjit, Hanusch, Franziska and Inoue, Shigeyoshi;
  • Item type:Article
    ID code:73449
    Dates:
    Date
    Event
    14 May 2020
    Published
    21 April 2020
    Published Online
    7 April 2020
    Accepted
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:04 Aug 2020 14:00
    Last modified:18 Dec 2024 15:05
    URI:https://strathprints.strath.ac.uk/id/eprint/73449
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