Dialumenes – aryl vs. silyl stabilisation for small molecule activation and catalysis
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: https://orcid.org/0000-0001-5643-9256, Porzelt, Amelie, Bag, Prasenjit, Hanusch, Franziska and Inoue, Shigeyoshi;-
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Item type: Article ID code: 73449 Dates: DateEvent14 May 2020Published21 April 2020Published Online7 April 2020AcceptedSubjects: Science > Chemistry Department: Faculty of Science > Pure and Applied Chemistry Depositing user: Pure Administrator Date deposited: 04 Aug 2020 14:00 Last modified: 11 Nov 2024 12:46 URI: https://strathprints.strath.ac.uk/id/eprint/73449